Hydrophobic group-containing copolymer and process for the production thereof

ABSTRACT

[Objective] This invention is to provide a novel copolymer suitably applicable to a detergent composition having an excellent precipitation inhibitory ability and showing a good washing effect even under severe conditions of washing with water used to take Japanese bath. [Solution] A laundry detergent or cleaning composition which comprises a hydrophobic group-containing copolymer characterized by having 1 wt % or more but below 50 wt % of a structural unit (a) derived from at least one kind of monomer (A) selected from ether bond-containing monomers.

TECHNICAL FIELD

This invention pertains to a hydrophobic group-containing copolymer andprocess for the production of it.

BACKGROUND ART

Previously, detergents used for washing of clothes, etc., were beingcompounded with detergent builders (detergent aids) such as zeolite,carboxymethylcellulose, polyethylene glycol, etc., for the purpose ofimproving the washing effects of detergents.

In addition to various detergent builders described above, detergentcompositions have been being compounded with polymers as a detergentbuilder.

For example, it has been reported to use (meth)acrylic acid-typepolymers comprising (meth)acrylic acid-type monomers,2-hydroxyethyl(meth)acrylate, C₂₋₁₂ alkyl(meth)acrylate and/or vinylaromatic monomers in detergent builders and detergent compositions(e.g., refer to Patent Reference 1). The copolymer compositionsdescribed in the above patent reference 1 are disclosed to have effectsof effective removal of hydrophobic dirt and stains of clothing such ascollar dirt, oily stains, etc., and excellent resoil inhibiting abilitypreventing the dirt or stains once removed from reattaching to thewashings even if the washing is carried out with a small amount ofwater.

Furthermore, it has been also disclosed to use polyalkylene glycol-typepolymers having a glycidyl ether-origin hydrophobic site inside thechain and/or at the chain end, monomer unit derived from a polyalkyleneglycol-type monomer with a polymeric double bond of an isoprenol, allylalcohol or methallyl alcohol origin and at the same time, carboxylicacid group and/or sulfonic acid group as a detergent builder (refer toPatent Reference 2). In the patent reference 2, the above polymers havebeen disclosed to have a performance inhibiting precipitation of thesurfactant and/or ability inhibiting resoiling with dirt removed once atthe time of washing (called resoil inhibitory ability).

Furthermore, as a property presently required for detergent builders,there are not only abilities improving the detergency of detergents butalso performance inhibiting or preventing any precipitation of thesurfactant (it may be called simply precipitation inhibitory ability,below). In this case, the problem of surfactant precipitation isapparent as a result of bonding of anionic surfactants, for example,straight chain alkylbenzenesulfonic acids (salt (LAS) such asdodecylbenzenesulfonic acid (salt), etc., with calcium or magnesium ionpresent in water when the washing is carried out with water ofrelatively high hardness (refer to Non-patent Reference 1).

As an art improving the precipitation inhibitory ability, there is atechnique disclosed in Patent Reference 3. In the patent reference 3, agraft copolymer of a hydrocarbon group-containing polyoxyalkylenecompound with a specific amount of an acid group-containing unsaturatedmonomer graft-polymerized is shown to exhibit an excellent performanceas a detergent builder.

CITATION LIST Patent Literature

-   [PTL 1] Japanese Patent Publication (Kokai) No. 2007-231262-   [PTL 2] WO2007/037469-   [PTL 3] Japanese Patent Publication (Kokai) No. 2007-254679

Non-Patent Literature

-   [NPL 1] Louis Ho Tan Tai, “Formulating Detergents and Personal Care    Products”, AOCS Press, pp. 52-54 (2000).

SUMMARY OF THE INVENTION Technical Problem

In spite of various polymers reported previously as described above,there has been no polymer exhibiting any satisfactory effect ofprecipitation inhibitory ability to date in the case of applications indetergents.

Therefore, this invention has been carried out considering thecircumstances as described above, and its objective is to provide apolymer (or polymer composition) being able to inhibit any precipitationof the surfactant effectively in the case of detergent applications.

Another objective of this invention is to provide an effective processfor the production of the above polymer (or polymer composition).

Solution Problem

The inventors of this invention studied diligently on various polymers(including copolymers) to accomplish the above objectives, and as aresult, they found that a copolymer (hydrophobic group-containingcopolymer) having a constituting unit originated from an etherbond-containing relatively hydrophobic monomer and carboxylgroup-containing monomer-origin constituting unit in a specificproportion showed an excellent precipitation inhibitory ability(performance inhibiting/preventing precipitation of surfactants). Thisinvention has been successfully carried out based on the above finding.

Specifically, this invention is a hydrophobic group-containing copolymercharacterized by having 1 wt % or more but 50 wt % or less of astructural unit (a) derived from at least one kind of monomer (A)selected from ether bond-containing monomers represented by thefollowing formulas (1) and (2);

in the above formula (1), R₀ is a hydrogen atom or CH₃ group, R is a CH₂group, CH₂CH₂ group or single bond, X is a number in the range of 0-5(provided X is a number in the range of 1-5 if R is a single bond), andR₁ is a hydrogen atom or organic group having 1-20 carbon atoms;

in the above formula (2), R₀ is a hydrogen atom or CH₃ group, R is a CH₂group, CH₂CH₂ group or single bond, X is a number in the range of 0-5,and R₁ is a hydrogen atom or organic group having 1-20 carbon atoms; and50 wt % or more but 99 wt % or less of a structural unit (b) derivedfrom a carboxyl group-containing monomer (B) as an essentialconstituting unit.

Advantageous Effects of Invention

The hydrophobic group-containing copolymer (or polymer composition) ofthis invention shows an excellent precipitation inhibitory ability(performance inhibiting/preventing precipitation of surfactants), andconsequently, if the hydrophobic group-containing copolymer of thisinvention is used in a detergent composition, the precipitation of thesurfactant of the detergent is effectively inhibited.

DESCRIPTION OF EMBODIMENTS

This invention is explained in detail as follows.

[Hydrophobic Group-Containing Copolymer of this Invention]

<Ether Bond-Containing Monomer as the Monomer (A)>

The hydrophobic group-containing copolymer of this invention isessentially required to have a specific proportion of a structural unit(a) originated from at least one kind of monomer (A) selected from etherbond-containing monomers represented by the following formulas (1) and(2).

In the above formula (1), R₀ is a hydrogen atom or CH₃ group, R is a CH₂group, CH₂CH₂ group or single bond, X is a number in the range of 0-5(provided X is a number in the range of 1-5 if R is a single bond), andR₁ is a hydrogen atom or organic group having 1-20 carbon atoms.

In the above formula (2), R₀ is a hydrogen atom or CH₃ group, R is a CH₂group, CH₂CH₂ group or single bond, X is a number in the range of 0-5,and R₁ is a hydrogen atom or organic group having 1-20 carbon atoms.

In the formula (1), R is preferably a CH₂CH₂ group because of a higheffect improving the precipitation inhibitory ability of the copolymerprepared, and in the formula (2), R is preferably a CH₂ group because ofa high effect improving the precipitation inhibitory ability of thecopolymer prepared.

In the formulas (1) and (2), R₁ is a hydrogen atom or organic grouphaving 1-20 carbon atoms, but R₁ is preferably an organic group having4-18 carbon atoms, and it is optimally an organic group having 6-16carbon atoms. R₁ may contain a functional group such as amino amide,hydroxyl, alkoxide, sulfonic acid, carbonyl, carboxyl, etc. R₁ may alsocontain ether bonding, sulfide bonding, ester bonding or amide bonding.The organic group is preferably an alkyl, aryl or alkenyl group.

As a preferable group for R₁, there are, for example, alkyl groups suchas n-butyl, isobutyl, octyl, lauryl, stearyl, cyclohexyl and2-ethylhexyl; alkenyl groups such as butylene, octylene, nonylene, etc.;and aryl groups such as phenyl, phenethyl, 2,3- or 2,4-xylyl, mesityl,naphthyl, etc.

As a preferable monomer of the formula (1), there are those compoundsrepresented by the following formulas (3)-(7). Those compoundsrepresented by the formulas (3)-(7) are preferably prepared by carryingout the reactions of allyl alcohol or isoprenol with corresponding 1)alkyl halides, 2) epoxy compounds, 3) glycidyl compounds, 4) estercompounds or 5) isocyanate compounds.

In the formulas (3)-(7), R₀ is a hydrogen atom or CH₃ group, R and X aresame as those in the formula (1). Furthermore, R₂ is an alkyl grouphaving 1-20 carbon atoms, alkenyl group or aryl group.

As a preferable monomer of the formula (2), there are, for example,those compounds represented by the formulas (8)-(9). The compoundsrepresented by the formulas (8)-(9) are preferably prepared by carryingout the reactions of allyl glycidyl ether with corresponding 1) alcoholsor their alkylene oxide adducts or 2) amines.

In the formulas (8) and (9), R₀ is a hydrogen atom or CH₃ group, R and Xare same as those in the formula (2). Furthermore, R₂ and R₃ are analkyl groups having 1-20 carbon atoms, alkenyl groups or aryl groups.

The monomer (A) contains preferably no ester or amide group so that thehydrophobic group-containing copolymer of this invention exhibits itsstable ability inhibiting precipitation under an alkaline condition.

In the above constituting unit (a), the unsaturated double bonding(CH₂═CH—) in the monomer (A), that is, the above formula (1) or (2)becomes in a form of single bonding (—CH₂—CH—).

The hydrophobic group-containing copolymer of this invention isessentially required to have 1 wt % or more but below 50 wt %, on 100 wt% of the total amount of monomer-origin structures, of the a structuralunit (a) derived from at least one kind of monomer (A) selected fromether bond-containing monomers represented by the above formulas (1) and(2). In this invention, the monomer is a compound having an unsaturateddouble bond (carbon-carbon double bond). If the proportion of thestructural unit (a) is the above range, the effect improving theprecipitation inhibition ability of the copolymer is excellent. Theproportion of the structural unit (a) on 100 wt % of the total amount ofmonomer-origin structures is preferably 2 wt % or more but below 40 wt%, and it is optimally 3 wt % or more but below 30 wt %. As a result ofthe hydrophobic group-containing copolymer of this invention having themonomer (A)-origin structure unit (a) in the above range, theprecipitation inhibition ability is improved.

As a result of the hydrophobic group-containing copolymer of thisinvention having a relatively hydrophobic structural unit (a)introduced, the hydrophobic group-containing copolymer can improve theinteraction with the surfactant becoming able to inhibit theprecipitation of the surfactant. Furthermore, the copolymerization ofthe monomer (A) with the monomers (B) and (C) is carried out relativelyeasily even in a hydrophilic solvent such as water, etc., andconsequently, it is possible to improve the precipitation inhibitionability of the hydrophobic group-containing copolymer prepared markedly.

<Carboxyl Group-Containing Monomer>

The hydrophobic group-containing copolymer of this invention isessentially required to have a carboxyl group-containing monomer(B)-origin structural unit (b) in a specific proportion.

The carboxyl group-containing monomer (B) of this invention is a monomeressentially having 1) unsaturated double bond and 2) carboxyl groupand/or salt [those monomers belonging to the monomer (A) or monomer (C)are excluded from the monomer (B)]. Specifically, there are, forexample, unsaturated monocarboxylic acids or salts such as acrylic acid,methacrylic acid, crotonic acid, α-hydroxyacrylic acid,α-(hydroxymethyl)acrylic acid, their derivatives, etc.; and unsaturateddicarboxylic acids and salts such as itaconic acid, fumaric acid, maleicacid, etc. The unsaturated dicarboxylic acid-type monomer in this casemay be a monomer having a single unsaturated bond and two carboxylicgroups, and preferred specific examples include maleic acid, itaconicacid, citraconic acid, fumaric acid, their univalent metal salts,divalent metal salts, ammonium salts, organic ammonium salts (organicamine salts) and anhydrides. Furthermore, the (meth)acrylic acid-typemonomers may be half-esters of unsaturated dicarboxylic acid-typemonomers with alcohols having 1-22 carbon atoms; half-amides ofunsaturated dicarboxylic acid-type monomers with amines having 1-22carbon atoms; half-esters of unsaturated dicarboxylic acid-type monomerswith glycols having 2-4 carbon atoms; half-amides of maleamic acid withglycols having 2-4 carbon atoms; etc.

As a salt of unsaturated mono- or dicarboxylic acid, there are metalsalts, ammonium salts and organic amine salts. As a metal salt in thiscase, there are univalent metal salts of alkaline metals such as sodium,lithium, potassium, rubidium, cesium, etc.; alkaline earth metals suchas magnesium, calcium, strontium, barium, etc.; and elements such asaluminum, iron, etc. As an organic amine salt, there are organic aminesalts of alkanolamines such as monoethanolamine, diethanolamine,triethanolamine, etc., and polyamines such as ethylenediamine,triethylenediamine, etc. The use of ammonium, sodium or potassium saltsamong them is preferable because of high effects improving theprecipitation inhibitory performance of the copolymer prepared, and theuse of sodium salts is optimal.

The use of acrylic acid, acrylate, maleic acid or maleate among thecarboxyl group-containing monomers (B) is preferable because of thecopolymer prepared providing a high effect improving the precipitationinhibitory performance, and the essential use of acrylic acid oracrylate is optimal.

In the case of a carboxyl group-containing monomer (B), it is possibleto use only 1 kind of the monomer, but the structure may be derived from2 or more kinds of the monomers. In this case, the hydrophobicgroup-containing copolymer of this invention has the total of thestructural unit (b) originated from all kinds of the carboxylgroup-containing monomers (B) used in a specific proportion.

In the above structural unit (b), the unsaturated double bonding(CH₂═CH—) in the monomer (B) becomes in a form of single bonding(—CH₂—CH—).

The hydrophobic group-containing copolymer of this invention isessential to contain 50 wt % or more but below 99 wt % of the carboxylgroup-containing monomer (B)-origin structural unit (b) on 100 wt % ofthe total monomer-origin structures. If the proportion of the structuralunit (b) is within the above range, the copolymer prepared provides anexcellent effect for improving the precipitation inhibitory performance.The proportion of the structural unit (b) on the 100 wt % of the totalmonomer-origin structures is preferably 60 wt % or more but below 98 wt%, and optimally, it is 70 wt % or more butt below 97 wt %.

If the hydrophobic groups-containing copolymer of this invention is usedas a detergent builder, the water solubility of the polymer is improvedbecause of the structural unit (b) contained in a specific proportion,and because of the structural unit (a), it can provide an inhibitoryeffect on surfactant precipitation.

Incidentally, in the case of computation of a proportion by weight (wt%) of the carboxyl group-containing monomer (B)-origin structural unit(b) on the total monomer-origin structures in this invention, thecomputation is carried out as the corresponding acid. For example, inthe case of a sodium acrylate-origin structural unit —CH₂—CH(COONa)—,the computation is carried out for the proportion by weight (wt %) of anacrylic acid-origin unit —C₁₋₁₂—CH(COOH)—. Similarly in the case of aproportion by weight (wt %) of the carboxyl group-containing monomer (B)on the total monomers, the computation is carried out as thecorresponding acid. For example, in the case of a sodium acrylate, thecomputation is carried out for the proportion by weight (wt %) asacrylic acid.

Furthermore, in the case of computation of a proportion by weight (wt %)of a structural unit originated from an acid group-containing monomerother than the carboxyl group-containing monomer (B) on the totalmonomer-origin structures, the computation is to be carried out as thecorresponding acid; and in the case of computation of a proportion byweight (wt %) of an acid group-containing monomer other than thecarboxyl group-containing monomer (B) on the total monomers, thecomputation is to be carried out as the corresponding acid. In the caseof an amino group-containing monomer-origin structural unit and aminogroup-containing monomer, the weight computation is carried out as thecorresponding un-neutralized amine-origin structural unit andun-neutralized amine, respectively. For example, in the case of vinylamine hydrochloride, the proportion by weight (wt %) is calculated as avinyl amine, which is the un-neutralized amine.

<Other Monomer>

The hydrophobic group-containing copolymer of this invention may haveanother monomer (C)-origin structural unit (C).

The monomer (C) in case the hydrophobic group-containing copolymer ofthis invention contain another monomer (C) is not especially restrictedas long as it is copolymerizable with the above monomer (A) and/or (B),and it is selected depending on the effect desired. Specifically, thereare, for example, sulfonic acid group-containing monomers such asvinylsulfonic acid, styrenesulfonic acid, allylsulfonic acid,methallylsulfonic acid, acryladmide-2-methylpropanesulfonic acid, sodium2-hydroxyl-3-allyloxypropanesulfonate, sodium2-hydroxyl-3-methallyloxypropanesulfonate, isoprenesulfonic acid,sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate,sulfopropyl methacrylate, 2-hydroxyl-3-butenesulfonic acid, etc., andtheir salts; N-vinyl monomers such as N-vinylpyrrolidone,N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide,N-vinyl-N-methylacetamide, N-vinyloxasolidone, etc.; amide-type monomerssuch as (meth)acrylamide, N,N-dimethylacrylamide, N-isopropylacrylamide,etc.; alkyl (meth)acrylate monomers such as butyl (meth)acrylate,2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, etc.; hydroxylgroup-containing monomers such as 3-(meth)allyloxy-1,2-dihydroxypropane,3-allyloxy-1,2-dihydroxypropane, 3-allyloxy-1,2-dihydroxypropane,(meth)ally alcohol, isoprenol, etc., with 6-200 moles of ethylene oxideadded (3-allyloxy-1,2-di(poly)oxyethylene ether propane, etc.);polyalkylene glycol (meth)acrylate, etc.; hydroxyalkyl (meth)acrylatetype monomers such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl(meth)acrylate, hydroxybutyl (meth)acrylate, 2-hydroxybutyl(meth)acrylate, 4-hydroxybutyl (meth)acrylate, α-hydroxymethylethyl(meth)acrylate, hydroxypentyl (meth)acrylate, hydroxyneopentyl(meth)acrylate, hydroxyhexyl (meth)acrylate, etc.; vinyl allyl monomerssuch as styrene, indene, vinylaniline, etc.; isobutylene, vinyl acetate,etc.

Furthermore, the above other monomer (C) may be used alone as a singlekind or a mixture of 2 or more kinds.

The hydrophobic group-containing copolymer of this invention has theabove constituting units (a) and (b) and if necessary, constituting nit(c) in the above specific proportions, and the respective constitutingunits may be present either in a block or random state. Furthermore, themean weight-average molecular weight of the hydrophobic group-containingcopolymer of this invention is suitably settable, and it is notespecially restricted. Specifically, the weight-average molecular weightof the hydrophobic group-containing copolymer of this invention isgenerally in the range of 2,000-200,000, preferably 30,000-60,000 andoptimally 4,000-30,000. If the weight-average molecular weight is withinthe above range, the precipitation inhibitory ability is liable to beimproved. Incidentally, the weight-average molecular weight in thisspecification is defined as a result of measurement with GPC (gelpermeation chromatography), and the computation is carried out with thespecific measurement method described in the application example.

The hydrophobic group-containing copolymer of this invention hasexcellent ability inhibiting precipitation of surfactants, and it isapplicable to, for example, detergent compositions.

[Hydrophobic Group-Containing Copolymer Composition (it may be SimplyCalled as a Polymer Composition, Below)]

The hydrophobic group-containing copolymer composition of this inventioncontains the hydrophobic group-containing copolymer of this invention asan essential component, the use of any component other than thehydrophobic group-containing copolymer of this invention is optional,but in general, it contains one or more of other components such aspolymerization initiator residue, residual monomer, polymerizationreaction byproduct and moisture content. The hydrophobicgroup-containing copolymer composition of this invention has apreferable configuration containing 30-80 wt % of the hydrophobicgroup-containing copolymer of this invention and 20-70 wt % of water.

[Process for the Production of the Hydrophobic Group-ContainingCopolymer of this Invention]

The process for the hydrophobic group-containing copolymer of thisinvention may be a known process for the polymerization reaction used asit is or after slight modification. In the process for the production ofthe hydrophobic group-containing copolymer of this invention, thecopolymerization of monomer components containing the etherbond-containing monomer (A) and carboxyl group-containing monomer (B),respectively as an essential component is carried out to obtain theproduct. Furthermore, the copolymerization reaction of those monomercomponents may be carried out with the above other monomer (C) as anoptional component.

In the above process for the production, the copolymerization reactionof the monomer components may be carried out with a polymerizationinitiator.

Incidentally, the kinds and amounts of the monomers contained in themonomer components are to be suitably adjusted so that the constitutingunits forming the hydrophobic group-containing copolymer of thisinvention are those described above. Specifically, the contentproportions of the monomers consisting the hydrophobic group-containingcopolymer of this invention are, on the total amount of the monomers, 1wt % or more but less than 50 wt % of the ether group-containing monomer(A) and 50 wt % or more but less than 99 wt % of the carboxylgroup-containing monomer (B). As described above, it is also possible touse another monomer (C), which is copolymerizable with these monomers,in the amount in the range of 0-10 wt % when the total amount of themonomers (A)-(B) is 100 wt %. Preferably, the proportion of the etherbond-containing monomer (A) is 2 wt % or more but less than 40 wt %, andthe proportion of the carboxyl group-containing monomer (B) is 60 wt %or more but less than 98 wt %. Furthermore, in the optical case, it isto use 3 wt % or more but less than 30 wt % of the ether bond-containingmonomer (A) with 70 wt % or more but less than 97 wt % of the carboxylgroup-containing monomer (B). The total amount of the above monomers(A), (B) and (C) is set at 100 wt %.

The copolymerization of the monomers (A)-(B) and if necessary, othermonomer (C) is preferably carried out with a solvent containing 50 wt %or more of water and/or in the presence of a chain-transfer agent, andoptimally, it is carried out with a solvent containing 50 wt % or moreof water in the presence of a chain-transfer agent. In this case, thesolvent used contains 50 wt % or more of water restricting the amount ofany organic solvent used in the polymerization reaction, andconsequently, there is an advantage of the removal of the organicsolvent by distillation after completing the polymerization reactionbeing easy. Furthermore, if the reaction is carried out in the presenceof a chain-transfer agent, the hydrophobic group-containing copolymer tobe prepared is inhibited from become a high molecular weight polymerhigher than necessary, and there is an advantage of being able to carryout effective manufacturing of the hydrophobic group-containingcopolymer of this invention having a low molecular weight. Especially,if the chain-transfer agent used is a sulfurous acid or sulfite, it ispossible to introduce a sulfonic acid group quantitatively at theterminal end of the hydrophobic group-containing copolymer, as explainedlater in detail, and the gel resistance is improved.

Therefore, the process for the production of this invention has apreferable configuration pertaining to a process for the production of ahydrophobic group-containing copolymer containing a stage to carry outcopolymerization by using 1 wt % or more but less than 50 wt % of theether bond-containing monomer (A) of the formula (1), 50 wt % or morebut less than 99 wt % of the hydroxyl group-containing monomer of theformula (2) and if necessary, another monomer (C) [provided the totalproportion of the monomers (A), (B) and (C) being 100 wt %]; allowingthe solvent used to contain 50 wt % or more of water; and furthermore,using a chain-transfer agent.

As a solvent usable in the above mode, there is no special restrictionas long as it contains 50 wt % or more of water on the total amount ofsolvent used. From the viewpoint of improving the solubility of themonomers used for the polymerization reactions in the solvent, anorganic solvent is also desirably used. Even in this case, the watercontent in the whole solvent mixture is 50 wt % or higher. As an organicsolvent usable in this case, there are, for example, lower alcohols suchas methanol, ethanol, isopropyl alcohol, etc.; lower ketones such asacetone, methyl ethyl ketone, diethyl ketone, etc.; ethers such asdimethyl ether, dioxane, etc.; and amides such as dimethylformamide,etc. In the case of these solvents used, the content of water ispreferably 80 wt % or higher on the total amount of solvent mixtureused, and the use of water alone (that is, 100 wt % water) is optimal.

In the process for the production of this invention, thecopolymerization reaction is preferably carried out in the presence of achain-transfer agent. The chain-transfer agent used in this case is notespecially restricted as long as it is a compound enabling molecularweight adjustment, and any of those know chain-transfer agents isusable. Specifically, there are, for example, thiol-type chain-transferagents such as mercaptoethanol, thioglycerol, thioglycolic acid,2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid,octyl thioglycolate, octyl 3-mercaptopropionate,2-mercaptoethanesulfonic acid, n-dodecyl mercaptan, octyl mercaptan,butyl thioglycolate, etc.; halides such as carbon tetrachloride,methylene chloride, bromoform, bromotrichloroethane, etc.; secondaryalcohols such as isopropanol, glycerol, etc.; and lower oxides and theirsalts such as phosphorous acid, hypophosphorous acid and their salts(sodium hypophosphate, potassium hypophosphate, etc.), sulfurous acid,hydrogen sulfurous acid, dithionous acid, metabisulfurous acid and theirsalts (sodium hydrogen sulfite, potassium hydrogen sulfite, sodiumdithionite, potassium dithionite, sodium metabisulfite, potassiummetabisulfite, etc.), etc. These chain-transfer agents may be used aloneor as a mixture of 2 or more kinds. The use of sulfurous acid orsulfites is suitable in the copolymerization reaction of this invention.As a result, it is possible to introduce a sulfonic acid groupquantitatively at the terminal end of the main chain of the hydrophobicgroup-containing copolymers and consequently improve the gel resistance.Incidentally, the quantitative introduction of a sulfonic acid groupsimplies the sulfite used being functioning very well as a chain-transferagent. Therefore, it becomes unnecessary to add the chain-transfer agentin an excess amount to the polymerization reaction system reducing thecopolymer production costs, at the same time, improving the productionefficiency and satisfactorily reducing the amount of impurities formed.Furthermore, as a result of the addition of a sulfite to thepolymerization reaction system, it is possible to inhibit the copolymerto have a high molecular weight higher than necessary.

In the process for the production described above, sulfurous acid and/orsulfite [simply called sulfurous acid (salt), below] is contained as achain-transfer agent. In addition to sulfurous acid (salt), apolymerization initiator is used in the process for the productiondescribed above. It is also possible to use a heavy metal ion as areaction promoter.

The above sulfurous acid (salt) is sulfurous acid, hydrogen sulfurousacid or their salt, and it is optimally in the form of a salt ofsulfurous acid or hydrogen sulfurous acid. If a sulfurous acid orhydrogen sulfurous acid is used, specific examples include those saltsdescribed above and metal atom salts, ammonium salts and organicammonium salts. As a metal atom in the metal atom salts, there are, forexample, univalent atoms of alkali metal elements such as lithium,sodium, potassium, etc.; divalent atoms of alkaline earth metal elementssuch as calcium, magnesium, etc.; and trivalent metal atoms of elementssuch as aluminum, iron, etc. Furthermore, as an organic ammonium(organic amine), there are suitably alkanol amines such as ethanolamine,diethanolamine, triethanolamine, etc., triethylamine, etc. In additionammonium sulfite is also usable. Therefore, as a sulfite preferablyusable in this invention, there are, for example, sodium hydrogensulfite, potassium hydrogen sulfite, ammonium hydrogen sulfite, sodiumsulfite, potassium sulfite, ammonium sulfite, etc., and the use ofsodium hydrogen sulfite is optimal. Those sulfuric acid (salt) compoundsare usable alone or as a mixture of 2 or more kinds.

The amount of a chain-transfer agent to be added in the process of thisinvention is not especially restricted as long as the polymerization ofthe monomers (A) and (B) and if necessary, monomer (C), but preferablyit is in the range of 1-20 g, optimally 2-15 g per mole of the wholecontent of the monomers (A) and (B) and if necessary, monomer (C). If itis less than 1 g, there may be a difficulty controlling the molecularweight, on the other hand, if it is over 20 g, the amount of impuritiesformed is increased causing a risk of reducing the purity of the polymerprepared, and especially in the case of a sulfite used, any excessamount of the sulfite is decomposed inside the reaction system causing arisk of generating sulfurous acid gas. In addition, there is also a riskof causing an economical disadvantage.

As an initiator, any of those previously known initiators is usable,there are, for example, hydrogen peroxide; persulfates such as sodiumpersulfate, potassium persulfate, ammonium persulfate, etc.; azocompounds such as 2,2′-azobis(2-amidinopropane) hydrochloride,4,4′-azobis(4-cyanovaleric acid), azobisisobutylonitrile,2,2′-azobis(4-methoxyl-2,4-dimethylvaleronitrile), etc.; and organicperoxides such s benzoyl peroxide, lauroyl peroxide, peracetic acid,di-t-butyl peroxide, cumen hydroperoxide, etc. The use of hydrogenperoxide and persulfates among these polymerization initiator ispreferably, and the use of persulfates is optimal. These polymerizationinitiators may be used alone or as a mixture of 2 or more kinds.

The amount of a polymerization initiator to be used is not especiallyrestricted as long as it is sufficient to start the copolymerizationreaction of the monomers (A) and (B) and if necessary, monomer (C), butit is generally below 10 g, preferably in the range of 1-5 g per mole ofthe total monomer components such as monomers (A) and (B) and ifnecessary monomer (C).

The heavy metal ion used in the reaction promoter of this invention is ametal ion of metal having specific gravity of 4 g/cm³ or higher.Specific examples of the metal of such a metal ion includes preferablyiron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver,gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium,etc. These heavy metals are usable alone or as a mixture or 2 or morekinds. The use of iron among them is preferable. The ionic valency ofthese heavy metal ions is not especially restricted, and if the heavymetal used is iron, the iron ion in the initiator may be Fe²⁺, Fe³⁺ ortheir combination.

The state of the above heavy metal ion is not especially restricted aslong as it is present in an ionic form, but it is preferable to use asolution prepared by dissolving a heavy metal compound because of easyhandling. The heavy metal compound usable in this case may be anycompound containing the desired heavy metal ion desired to be containedin the initiator, and it may be determined depending on the specificinitiator to be used. If the above heavy metal ion is an iron,preferable examples of heavy metal compounds useable include Mohr salt[Fe(NH₄)₂(SO₄)₂.6H₂O], ferric sulfate heptahydrate, ferrous chloride,ferric chloride, etc. Furthermore, if heavy metal ion used is manganese,manganese chloride, etc., may be suitably used. These heavy metalcompounds are all water-soluble compounds, thus, it is possible to usedthem in the form of aqueous solutions, and consequently, thehandle-ability is excellent. Incidentally, the solvent used to dissolvethe above heavy metal compounds to prepare their solutions is notnecessarily limited to water, and it is possible to use any solvent aslong as it can dissolve the heavy metal compound and does not interferewith the polymerization reaction in the process for the production ofhydrophobic group-containing copolymer of this invention.

If the above heavy metal ion is to be used, the amount heavy metal ionis preferably a catalyst quantity in the polymerization process of thisinvention. The catalyst quantity in this specification means the amountacting as a catalyst and not incorporated in the desired final product.Specifically, it is below 100 ppm, preferably below 10 ppm and optimallybelow 5 ppm.

Furthermore, the content of the above heavy metal ion is preferably inthe range of 0.1-10 ppm on the total weight of the polymerizationreaction mixture at the time of the completion of the polymerizationreaction. If the content of the heavy metal ion is below 0.1 ppm, thereis a risk of the effect of the heavy metal ion added not being exhibitedsatisfactory. On the other hand, if the content of the heavy metal ionadded is over 10 ppm, there is a risk of the coloration of the copolymerprepared being damaged. Furthermore, if the heavy metal ion content ishigh, and the polymer product is used as a detergent builder, there is arisk of causing contamination in the detergent builder.

The above at the time of the completion of the polymerization reactionmeans the time point when the polymerization reaction has beenpractically completed in the polymerization reaction solution, and thedesired copolymer has been prepared. For example, if the polymer formedas a result of polymerization in the polymerization reaction mixturesolution is to be neutralized with an alkaline component, the content ofthe heavy metal ion is calculated based on the total weight of thepolymerization reaction solution after neutralization. If it containstwo or more kinds of heavy metal ions, the total amount of the heavymetal ions may be set in the above range.

In the case of combination of the above initiator and chain-transferagent, one kind or more each of the above persulfates and sulfites areoptimally used. In this case, the persulfate to sulfite mixing ratio isnot especially restricted, but 0.5-5 parts by weight of sulfite ispreferably used for 1 part by weigh of persulfate. Especially, the lowerlimit of sulfite is 1 part by weight per pat by weight of persulfate,and it is optimally 2 parts by weight. Furthermore, the upper limit ofsulfite is especially 3 parts by weight per part by weight ofpersulfate, and it is optimally 3 parts by weight. If the amount ofsulfite is below 0.5 part by weight, there is a risk of increasing thetotal amount of initiator to achieve a low molecular weight, on theother hand, if it is over 5 parts by weight, the extent of the sidereactions is increased causing a risk increasing the amount ofimpurities formed as a result.

The combination of the above chain-transfer agent, polymerizationinitiator and reaction promoter is not especially restricted, and thecompounds are suitably selected from those examples described above. Forexample, as a suitable combination of chain-transfer agent,polymerization initiator and reaction promoter, there are combinationssuch as sodium hydrogen sulfite (SBS)/hydrogen peroxide (H₂O₂), sodiumhydrogen sulfite (SBS)/sodium persulfate (NaPS), sodium hydrogen sulfite(SBS)/Fe, sodium hydrogen sulfite (SBS)/hydrogen peroxide (H₂O₂)/Fe,sodium hydrogen sulfite (SBS)/sodium persulfate (NaPS)/Fe, sodiumhydrogen sulfite (SBS)/sodium persulfate (NaPS)/hydrogen peroxide(H₂O₂), sodium hydrogen sulfite (SBS)/oxygen/Fe, etc. The combination ispreferably sodium hydrogen sulfite (SBS)/sodium persulfate (NaPS) orsodium hydrogen sulfite (SBS)/sodium persulfate (NaPS)/Fe, and it isoptimally sodium hydrogen sulfite (SBS)/sodium persulfate (NaPS)/Fe.

The total amount of the above chain-transfer agent, polymerizationinitiator and reaction promoter is in the range of 2-20 g per mole ofthe total monomer components, that is, monomers (A) and (B) and ifnecessary, monomer (C). As a result of the total amount within thisrange, it is possible to prepare the hydrophobic group-containingcopolymer of this invention efficiently, and furthermore, the molecularweight distribution of the hydrophobic group-containing copolymer can beset in a desired range. It is preferably in the range of 4-18 g, and itis optimally in the range of 6-15 g.

The above polymerization initiator and chain-transfer agent are added tothe reactor with a suitable method such as dripping, split addition,etc. Furthermore, the reactor may be charged with the chain-transferagent alone, or it may be mixed in advance with the monomer components,that is, monomers (A)-(B) and if necessary, monomer (C) and otherreaction components such as solvent, etc.

In the copolymerization process described above, the reactor is chargedwith the monomer components, polymerization initiator, etc., as follows.Specifically, it is possible to use a method charging the reactor withall monomer components and subsequently adding the polymerizationinitiator to start and carry out the copolymerization reaction; methodcharging the reactor with a portion of the monomer components andsubsequently adding the remaining portion of the monomer components andpolymerization initiator continuously or in steps (preferablycontinuously) to carry out the copolymerization reaction; methodcharging the reactor with the polymerization solvent alone andsubsequently adding the whole amount of the monomer components andpolymerization initiator; method charging the reactor with a portion ofone of the monomers (A)-(B) [for example, monomer (B)] and subsequentlyadding the monomer (A), remaining portion of the monomer (B) and ifnecessary monomer (C) to the reactor (preferably continuously) to carryout the copolymerization reaction; etc. Among those methods, the use ofthe method adding the polymerization initiator and monomer components indrops to the reactor to carry out the copolymerization reaction ispreferable because it is possible to obtain a narrow (sharp) molecularweight distribution for the copolymer obtained, and the dispersibilityin the case of applications as a detergent builder is improved.

The above process for the copolymerization of this invention may becarried out with a conventionally used method such as solution, bulk,suspension or emulsion polymerization, and there is no specialrestriction, but the use of solution polymerization is preferable. Asdescribed above, the solvent used in this case is preferably a solventmixture containing water in the amount corresponding to 50 wt % or moreon the total amount of solvent used or water. If water alone it to beused, it is suitably convenient because it is possible to eliminate asolvent removal stage.

The copolymerization process of this invention described above may becarried out in a batch or continuously. Furthermore, at the time ofcopolymerization, a known suitable solvent selectable from those knownsolvents may be used if necessary. It is suitably possible to use water;alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol,isopropyl alcohol, etc.; glycerol; polyethylene glycol, glycol, etc.;aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene,cyclohexane, n-heptane, etc.; esters such as ethyl acetate, etc.;ketones such as acetone, methyl ethyl ketone, etc.; amides such asdimethylformamide, etc.; and ethers such as diethyl ether, dioxane, etc.These solvents may be used alone or concomitantly as a mixture of 2 ormore kinds. Considering the solubility of the monomers and copolymers tobe prepared, it is preferable to use 1, 2 or more kind of solventsselected from water and lower alcohols having 1-4 carbon atoms.

The amount of the above solvent to be used is in the range of 40-200 wt% on 100 wt % of the monomers. It is preferably 45 wt % or higher,optimally 50 wt % or higher. Furthermore, it is preferably below 180 wt%, optimally below 150 wt %. If the amount of the solvent used is below40 wt %, there is a risk of the molecular weight of the copolymerprepared to be increased too high, on the other hand, if it is over 200wt %, there is a risk of the concentration of the copolymer preparedbecoming so low that it is required to carry out solvent removalprocedures. Incidentally, the reactor may be charged with the whole orpartial amount of the solvent in the initial period of thepolymerization reaction, a portion of the solvent may be added (indrops) to the reaction system during the polymerization reaction, or themonomers, initiator, etc., may be dissolved in the solvent, and thesolvent may be added (in drops) together with these components to thereaction system during the polymerization reaction.

In the copolymerization process described above, the copolymerizationreaction conditions such as temperature, etc., are suitably setdepending on the copolymerization method, solvent and initiator used,and the copolymerization temperature is generally 0° C. or above, butbelow 150° C. It is preferably 40° C. or above and optimally 80° C. orabove, but it is preferably below 120° C. and optimally below 110° C.Especially in the case of sulfurous acid (salt) being used, thecopolymerization temperature is generally in the range of 60-95° C.,preferably 70-95° C. and optimally 80-95° C. If it is below 60° C.,there is a risk of a large amount of sulfurous acid (salt)-originimpurities being formed. On the other hand, if is over 95° C., there isa risk of toxic sulfurous acid gas being released.

The above copolymerization temperature is not necessarily required tomaintain always at a constant level. For example, the polymerizationreaction may be started at room temperature, the temperature issubsequently raised to the desired temperature at a suitabletemperature-raising speed or time, and the desired temperature issubsequently maintained, or alternatively, the temperature may beallowed to fluctuate (raising or reducing) during the polymerizationreaction depending on the method adding the monomers, initiator, etc.

The time for the above copolymerization reaction is generally in therange of 30-300 min, preferably 60-240 min and optimally 120-180 min.

The pressure of the reaction system in the above process for thecopolymerization reaction is any of normal pressure (atmosphericpressure), reduced pressure or added pressure, but considering themolecular weight of the copolymer to be prepared, the reaction ispreferably carried out under atmospheric pressure or added pressureafter sealing the reaction system. Furthermore, the reaction underatmospheric pressure is preferable with respect to facilities requiredsuch as pressure addition or reduction device, pressure-resistancereactor and piping system, etc. The atmosphere inside the reactionsystem may be air, but it is preferably an inert gas atmosphere, andprior to carrying out the polymerization reaction, the reaction systemis preferably flushed with an inert gas such as nitrogen.

The pH during the polymerization reaction in the above copolymerizationis generally acidic, and especially in the case of concomitant use ofpersulfate and sulfite in the reaction system, the polymerizationreaction is preferably carried out under an acidic condition. As aresult of the reaction being carried out under an acidic condition, theaqueous solution viscosity elevation in the polymerization reactionsystem is inhibitable, and the production of the copolymer can becarried out well. Furthermore, it becomes possible to carry out thereaction under a condition of a high concentration drastically improvingthe production efficiency. Specifically, it is possible to carry out thepolymerization reaction at a high concentration of the final solidcontent concentration over 40%, and it is possible to prepare the finalproduct showing the total residual monomer concentration below 15,000ppm. Furthermore, the polymerizability of the ether bond-containingmonomer can be improved.

Under the acidic condition described above, the pH of the reactionmixture during the polymerization reaction at 25° C. is generally in therange of 1-6, it is preferably below 5 and it is optimally below 3. Thecopolymer prepared with the above process for the copolymerizationreaction may be usable in detergent compositions as a component(detergent builder), but if necessary, the final product may beneutralized with an alkaline substance. As a preferable alkalinesubstance, there are, for example, inorganic salts such as hydroxides,chlorides, carbonates, etc., of uni- or divalent metals, organicammonium compounds (organic amines), etc.

The degree of neutralization in the case of copolymerization is suitablyadjustable with the initiator. For example, in the case of persulfateand sulfite concomitantly used, and the monomers can form salts, thecopolymerization reaction of the monomers is preferably carried out withthe degree of neutralization of the carboxyl group-containing monomerset in the range of 0-60 mol %. The degree of neutralization of amonomer in this case is represented by mol % of the monomer forming asalt if the total number of mol of the monomer is set at 100 mol %. Ifthe degree of neutralization of the monomer is over 60 mol %, thepolymerization rate in the copolymerization reaction stage is notincreased causing a risk of the molecular weight of the copolymerprepared to be reduced to too low or production efficiency beingreduced. It is preferably below 50 mol %, especially below 40 mol %,furthermore, below 30 mol %, especially desirably below 20 mol % andoptimally below 10 mol %.

As a method for carrying out copolymerization with the degree of monomerneutralization in the range of 0-60 mol %, for example in the case of anunsaturated carboxylic acid-type monomer, there is a method wherein theunsaturated carboxylic acid monomer may be used for the copolymerizationwithout any neutralization or neutralized with an alkaline substance toa form of salt such as sodium or ammonium salt with a degree ofneutralization in the range of 0-60 mol % before using in thecopolymerization reaction.

The hydrophobic group-containing copolymer of this invention prepared asdescribed above is usable as a water treatment agent, fiber treatmentagent, dispersant, detergent builder (or detergent compositioncomponent), scaling prevention agent (scaling inhibitor), metal ionsequestering agent, thickener, various kinds o binders, emulsifier,skin-care agent, hair-care agent, etc. As a detergent builder, it isapplicable to detergents used for various applications such as clothing,dish washing, house cleaning, hair washing, body washing,tooth-brushing, car-cleaning, etc.

<Water-Treatment Agent>

The hydrophobic group-containing copolymer (or polymer composition) ofthis invention is usable as a water-treatment agent. Thiswater-treatment agent may be compounded, if necessary, with othercomponents such as polymerized phosphate, phosphonate, anti-corrosionagent, slime-controlling agent, chelating agent, etc.

The above water-treatment agent is useful for scaling inhibitoryapplications in cooling water circulation system, boiler watercirculation system, seawater desalination plant, pulp digester, blackliquid concentration reactor, etc. This treatment agent may contain anoptionally suitable water-soluble polymer within a range causing noeffect on the performance and effect.

<Fiber-Treatment Agent>

The hydrophobic group-containing copolymer (or polymer composition) ofthis invention is usable as a fiber-treatment agent. The fiber-treatmentagent contains at least one component selectable from a group comprisingcoloring agents, peroxides and surfactants and hydrophobicgroup-containing copolymer (or polymer composition) of this invention.

The content of the hydrophobic group-containing copolymer of thisinvention in the above fiber-treatment agent is in the range of 1-100 wt%, preferably 5-100 wt % on the total amount of the fiber-treatmentagent. This treatment agent may contain an optionally suitablewater-soluble polymer within a range causing no effect on theperformance and effect.

A compounding example of this fiber-treatment agent close to a preferredembodiment of this invention is explained as follows. Thisfiber-treatment agent is applicable in fiber treatment process stagessuch as degumming, dyeing, bleaching and soaping. The coloring agents,peroxides and surfactants usable are those conventionally used infiber-treatment agents.

A preferable example of the fiber-treatment agent has a composition of 1part by weight of the compounding proportion of the hydrophobicgroup-containing copolymer of this invention compounded with 0.1-100parts by weight at least one component selectable from a groupcomprising coloring agents, peroxides and surfactants to improve, forexample, whiteness of fiber and coloring fastness and prevent unevencoloring.

The above fiber-treatment agent is applicable to any optionally suitablefibers. For example, there are cellulose-type fibers such as cotton,hemp, etc.; synthetic fibers such as Nylon, polyester, etc.; animalfibers such as wool, silk, etc.; semi-synthetic fibers such as rayon,etc.; their fabrics; and their mixed spun products.

If the above fiber-treatment agent is to be applied to the degummingstage, the composition contains preferably the hydrophobicgroup-containing copolymer of this invention, alkaline agent andsurfactant. In the case of applications to the bleaching stage, thecomposition contains preferably the hydrophobic group-containingcopolymer of this invention, peroxide and silicic acid-type chemicalsuch as sodium silicate as an alkaline bleach decomposition inhibitor.

<Inorganic Pigment Dispersant>

The hydrophobic group-containing copolymer (or polymer composition) ofthis invention is usable as a inorganic pigment dispersant. Thisinorganic pigment dispersant may contain other components such ascondensed phosphoric acid or its salt, phosphonic acid or phosphonateand poly(vinyl alcohol).

The content of the hydrophobic group-containing copolymer of thisinvention in the above inorganic pigment dispersant is in the range of5-100 wt % on the total amount of the inorganic pigment dispersant. Thecomposition may contain an optionally suitable water-soluble polymerwithin a range causing no effect on the performance and effect.

The above inorganic pigment dispersant exhibits its excellentperformance in the case of applications as a dispersant of inorganicpigments such as heavy or light calcium carbonate and clay used forpaper coating. For example, if a small amount of the inorganic pigmentdispersant is added to an inorganic pigment and the mixture is dispersedin water, it is possible to prepare a high-concentration inorganicpigment slurry such as calcium carbonate slurry having a highconcentration with low viscosity, high fluidity and good stability withtime for these properties.

The amount of the above inorganic pigment dispersant used in the case ofapplications of the above inorganic pigment dispersant as a dispersantof inorganic pigments is in the range of 0.05-2.0 parts by weight per100 parts by weight of inorganic pigment. As a result of the amount ofthe inorganic pigment dispersant being within the above range, it ispossible to achieve a satisfactory dispersing effect corresponding tothe amount added providing also an economical advantage.

<Laundry Detergent and Cleaning Compositions Use of the Copolymer>

The hydrophobic group-containing copolymer (or polymer composition) ofthis invention is usable in detergent compositions.

The content of the hydrophobic group-containing copolymer in detergentcompositions is not especially restricted. However, from the viewpointof allowing the copolymer to exhibit its excellent builder performance,the content of the hydrophobic group-containing copolymer is in therange of 0.1-20 wt %, preferably 0.3-15 wt % and optimally 0.5-10 wt %on the total amount of detergent composition.

The copolymers of the present invention may be utilized in laundrydetergents or cleaning compositions comprising a surfactant systemcomprising C₁₀-C₁₅ alkyl benzene sulfonates (LAS) and one or moreco-surfactants selected from nonionic, cationic, anionic or mixturesthereof. The selection of co-surfactant may be dependent upon thedesired benefit. In one embodiment, the co-surfactant is selected as anonionic surfactant, preferably C₁₂-C₁₈ alkyl ethoxylates. In anotherembodiment, the co-surfactant is selected as an anionic surfactant,preferably C₁₀-C₁₈ alkyl alkoxy sulfates (AE_(x)S) wherein x is from1-30. In another embodiment the co-surfactant is selected as a cationicsurfactant, preferably dimethyl hydroxyethyl lauryl ammonium chloride.If the surfactant system comprises C₁₀-C₁₅ alkyl benzene sulfonates(LAS), the LAS is used at levels ranging from about 9% to about 25%, orfrom about 13% to about 25%, or from about 15% to about 23% by weight ofthe composition.

The above-mentioned laundry detergent or cleaning composition preferablycomprises from about 1% to about 20% by weight of the hydrophobicgroup-containing copolymer composition.

The surfactant system may comprise from 0% to about 7%, or from about0.1% to about 5%, or from about 1% to about 4% by weight of thecomposition of a co-surfactant selected from a nonionic co-surfactant,cationic co-surfactant, anionic co-surfactant and any mixture thereof.

Non-limiting examples of nonionic co-surfactants include: C₁₂-C₁₈ alkylethoxylates, such as, NEODOL® nonionic surfactants from Shell; C₆-C₁₂alkyl phenol alkoxylates wherein the alkoxylate units are a mixture ofethyleneoxy and propyleneoxy units; C₁₂-C₁₈ alcohol and C₆-C₁₂ alkylphenol condensates with ethylene oxide/propylene oxide block alkylpolyamine ethoxylates such as PLURONIC® from BASF; C₁₄-C₂₂ mid-chainbranched alcohols, BA, as discussed in U.S. Pat. No. 6,150,322; C₁₄-C₂₂mid-chain branched alkyl alkoxylates, BAE_(x), wherein x is from 1-30,as discussed in U.S. Pat. No. 6,153,577, U.S. Pat. No. 6,020,303 andU.S. Pat. No. 6,093,856; alkylpolysaccharides as discussed in U.S. Pat.No. 4,565,647 Llenado, issued Jan. 26, 1986; specificallyalkylpolyglycosides as discussed in U.S. Pat. No. 4,483,780 and U.S.Pat. No. 4,483,779; polyhydroxy fatty acid amides as discussed in U.S.Pat. No. 5,332,528; and ether capped poly(oxyalkylated) alcoholsurfactants as discussed in U.S. Pat. No. 6,482,994 and WO 01/42408.

Non-limiting examples of semi-polar nonionic co-surfactants include:water-soluble amine oxides containing one alkyl moiety of from about 10to about 18 carbon atoms and 2 moieties selected from the groupconsisting of alkyl moieties and hydroxyalkyl moieties containing fromabout 1 to about 3 carbon atoms; water-soluble phosphine oxidescontaining one alkyl moiety of from about 10 to about 18 carbon atomsand 2 moieties selected from the group consisting of alkyl moieties andhydroxyalkyl moieties containing from about 1 to about 3 carbon atoms;and water-soluble sulfoxides containing one alkyl moiety of from about10 to about 18 carbon atoms and a moiety selected from the groupconsisting of alkyl moieties and hydroxyalkyl moieties of from about 1to about 3 carbon atoms. See WO 01/32816, U.S. Pat. No. 4,681,704, andU.S. Pat. No. 4,133,779.

Non-limiting examples of cationic co-surfactants include: the quaternaryammonium surfactants, which can have up to 26 carbon atoms include:alkoxylate quaternary ammonium (AQA) surfactants as discussed in U.S.Pat. No. 6,136,769; dimethyl hydroxyethyl quaternary ammonium asdiscussed in U.S. Pat. No. 6,004,922; dimethyl hydroxyethyl laurylammonium chloride; polyamine cationic surfactants as discussed in WO98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006;cationic ester surfactants as discussed in U.S. Pat. Nos. 4,228,042,4,239,660 4,260,529 and U.S. Pat. No. 6,022,844; and amino surfactantsas discussed in U.S. Pat. No. 6,221,825 and WO 00/47708, specificallyamido propyldimethyl amine (APA).

Nonlimiting examples of anionic co-surfactants useful herein include:C₁₀-C₂₀ primary, branched chain and random alkyl sulfates (AS); C₁₀-C₁₈secondary (2,3) alkyl sulfates; C₁₀-C₁₈ alkyl alkoxy sulfates (AE_(x)S)wherein x is from 1-30; C₁₀-C₁₈ alkyl alkoxy carboxylates comprising 1-5ethoxy units; mid-chain branched alkyl sulfates as discussed in U.S.Pat. No. 6,020,303 and U.S. Pat. No. 6,060,443; mid-chain branched alkylalkoxy sulfates as discussed in U.S. Pat. No. 6,008,181 and U.S. Pat.No. 6,020,303; modified alkylbenzene sulfonate (MLAS) as discussed in WO99/05243, WO 99/05242 and WO 99/05244; methyl ester sulfonate (MES); andalpha-olefin sulfonate (AOS).

The present invention may also relates to compositions comprising theinventive copolymers and a surfactant system comprising C₈-C₁₈ linearalkyl sulphonate surfactant and a co-surfactant. The compositions can bein any form, namely, in the form of a liquid; a solid such as a powder,granules, agglomerate, paste, tablet, pouches, bar, gel; an emulsion;types delivered in dual-compartment containers; a spray or foamdetergent; premoistened wipes (i.e., the cleaning composition incombination with a nonwoven material such as that discussed in U.S. Pat.No. 6,121,165, Mackey, et al.); dry wipes (i.e., the cleaningcomposition in combination with a nonwoven materials, such as thatdiscussed in U.S. Pat. No. 5,980,931, Fowler, et al.) activated withwater by a consumer; and other homogeneous or multiphase consumercleaning product forms.

In one embodiment, the cleaning composition of the present invention isa liquid or solid laundry detergent composition. In another embodiment,the cleaning composition of the present invention is a hard surfacecleaning composition, preferably wherein the hard surface cleaningcomposition impregnates a nonwoven substrate. As used herein“impregnate” means that the hard surface cleaning composition is placedin contact with a nonwoven substrate such that at least a portion of thenonwoven substrate is penetrated by the hard surface cleaningcomposition, preferably the hard surface cleaning composition saturatesthe nonwoven substrate. The cleaning composition may also be utilized incar care compositions, for cleaning various surfaces such as hard wood,tile, ceramic, plastic, leather, metal, glass. This cleaning compositioncould be also designed to be used in a personal care and pet carecompositions such as shampoo composition, body wash, liquid or solidsoap and other cleaning composition in which surfactant comes intocontact with free hardness and in all compositions that require hardnesstolerant surfactant system, such as oil drilling compositions.

In another embodiment the cleaning composition is a dish cleaningcomposition, such as liquid hand dishwashing compositions, solidautomatic dishwashing compositions, liquid automatic dishwashingcompositions, and tab/unit does forms of automatic dishwashingcompositions.

Automatic detergent compositions may comprise low foaming nonionicsurfactants (LFNIs). LFNI can be present in amounts from about 0.25% toabout 4%. LFNIs are most typically used in automatic detergents onaccount of the improved water-sheeting action (especially from glass)which they confer to the gel automatic detergents. Preferred LFNIsinclude nonionic alkoxylated surfactants, especially ethoxylates derivedfrom primary alcohols, and blends thereof with more sophisticatedsurfactants, such as thepolyoxypropylene/polyoxyethylene/polyoxypropylene reverse blockpolymers. The PO/EO/PO polymer-type surfactants are well-known to havefoam suppressing or defoaming action, especially in relation to commonfood soil ingredients such as egg. In a preferred embodiment, the LFNIis an ethoxylated surfactant derived from the reaction of a monohydroxyalcohol or alkylphenol containing from about 8 to about 20 carbon atoms,excluding cyclic carbon atoms, with from about 6 to about 15 moles ofethylene oxide per mole of alcohol or alkyl phenol on an average basis.A particularly preferred LFNI is derived from a straight chain fattyalcohol containing from about 16 to about 20 carbon atoms(C₁₆-C₂₀alcohol), preferably a C₁₈ alcohol, condensed with an average offrom about 6 to about 15 moles, preferably from about 7 to about 12moles, and most preferably from about 7 to about 9 moles of ethyleneoxide per mole of alcohol. Preferably the ethoxylated nonionicsurfactant so derived has a narrow ethoxylate distribution relative tothe average.

The LFNI can optionally contain propylene oxide in an amount up to about15% by weight. Certain of the block polymer surfactant compoundsdesignated PLURONIC® and TETRONIC® by the BASF-Wyandotte Corp.,Wyandotte, Mich., are suitable in gel automatic detergents of theinvention. LFNIs which may also be used include a C-18 alcoholpolyethoxylate, having a degree of ethoxylation of about 8, commerciallyavailable as “SLF-18 Poly-tergent” from BASF Corp.

Dish washing compositions may additionally contain a dispersant polymertypically in the range from 0 to about 25%, preferably from about 0.5%to about 20%, more preferably from about 1% to about 7% by weight of thedetergent. The dispersant polymer may be ethoxylated cationic diaminesor ethoxylated cationic polyamines described in U.S. Pat. No. 4,659,802.Other dispersant polymers suitable for use include co-polymerssynthesized from acrylic acid, maleic acid and methacrylic acid such asACUSOL® 480N supplied by Rohm & Haas and an acrylic-maleic (ratio 80/20)phosphono end group dispersant copolymers sold under the tradename ofAcusol 425N (E) available from Rohm & Haas. Polymers containing bothcarboxylate and sulphonate monomers, such as ALCOSPERSE® polymers(supplied by Alco) are also acceptable dispersant polymers. In oneembodiment an ALCOSPERSE® polymer sold under the trade name ALCOSPERSE®725, is a co-polymer of Styrene and Acrylic Acid with the followingstructure:

-   -   x:y=60:40, or 50:50, MW=8000.        ALCOSPERSE® 725 may also provide a metal corrosion inhibition        benefit.

Other dispersant polymers are low molecular weight modified polyacrylatecopolymers including the low molecular weight copolymers of unsaturatedaliphatic carboxylic acids disclosed in U.S. Pat. Nos. 4,530,766, and5,084,535 and European Patent Application No. 66,915, published Dec. 15,1982.

Dish washing compositions may utilize detergent builders to assist incontrolling mineral hardness and dispersancy. Inorganic as well asorganic builders can be used. Embodiment of such dish washing productcan be selected from the group consisting of phosphate, phosphateoligomers or polymers and salts thereof, silicate oligomers or polymersand salts thereof, aluminosilicates, magnesioaluminosiliates, citrate,methyl glycine diacetic acid and/or salts thereof, glutamatic diaceticacid and/or salts thereof and mixtures thereof. Phosphate detergentbuilders include, but are not limited to, the alkali metal, ammonium andalkanolammonium salts of polyphosphates. Silicate builders herein areany silicates which are soluble to the extent that they do not adverselyaffect spotting/filming characteristics of the gel detergentcomposition. Aluminosilicate builders can be used in the presentcompositions though are not preferred for automatic dishwashingdetergents. Carbonate builders include alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973. Various grades and types of sodium carbonateand sodium sesquicarbonate can be used, certain of which areparticularly useful as carriers for other ingredients, especially:detersive surfactants. Organic detergent builders include a wide varietyof polycarboxylate compounds. Other useful builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid,and carboxymethyloxysuccinic acid, the various I alkali metal, ammoniumand substituted ammonium salts of polyacetic acids such asethylenediaminetetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxydisuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof. Citratebuilders, e.g., citric acid and soluble salts thereof (particularlysodium salt), are polycarboxylate builders of particular importance forheavy duty laundry detergent and automatic dishwashing formulations dueto their availability from renewable resources and theirbiodegradability. Methyl glycine diacetic acid and/or salts thereof(MGDA) may also be utilized as builders in the present composition. Apreferred MGDA compound is a salt of methyl glycine iacetic acidSuitable salts include the diammonium 1.0 slt, the dipotassium salt and,preferably, the disodium salt. Glutamatic diacetic acid and/or saltsthereof (GLDA) may also be utilized as builders in the presentcompositions. A preferred GLDA compound is a salt of glutamic diaceticacid. Suitable salts include the diammonium salt, the dipotassium saltand, preferably, the disodium salt. 1-hydroxyethylidene-1,1-diphosphonicacid (HEDP) may also be utilized as a builder in the presentcompositions.

Perfume may be added to the compositions of the present invention. Thedetergent compositions can contain agents that are effective ascorrosion inhibitors and/or anti-tarnish aids.

“Detergent enzyme”, as used herein, means any enzyme having a cleaning,stain removing or otherwise beneficial effect in a gel detergentcomposition. Preferred enzymes are hydrolases such as proteases,amylases and lipases. Highly preferred for automatic dishwashing areamylases and/or proteases, including both current commercially availabletypes and improved types. Enzyme-containing compositions herein cancomprise from about 0.001% to about 10%, preferably from about 0.005% toabout 8%, most preferably from about 0.01% to about 6%, by weight of anenzyme.

The compositions herein can also optionally contain one or moretransition-metal selective sequestrants, “chelants” or “chelatingagents”, e.g., iron and/or copper and/or manganese chelating agents.Chelating agents suitable for use herein can be selected from the groupconsisting of aminocarboxylates, phosphonates (especially theaminophosphonates), polyfunctionally-substituted aromatic chelatingagents, and mixtures thereof. Commercial chelating agents for use hereininclude the BEQUEST series, and chelants from Monsanto, DuPont, andNalco, Inc.

The detergent composition can be preferably low foaming, readily solublein the washing medium and most effective at pH values best conducive toimproved cleaning performance, such as in a range of desirably fromabout pH 6.5 to about pH 12.5, and preferably from about pH 7.0 to aboutpH 12.0, more preferably from about pH 8.0 to about pH 12.0. The pHadjusting components are desirably selected from sodium or potassiumhydroxide, sodium or potassium carbonate or sesquicarbonate, sodium orpotassium silicate, boric acid, sodium or potassium bicarbonate, sodiumor potassium borate, and mixtures thereof.

An embodiment of the present invention relates to a gel detergentcomposition comprising an organic solvent selected from the groupconsisting of low molecular weight aliphatic or aromatic alcohols, lowmolecular weight alkylene glycols, low molecular weight alkylene glycolethers, low molecular weight esters, low molecular weight alkyleneamines, low molecular weight alkanolamines, and mixtures thereof.

Any adjunct ingredient in any amount may be used in the gel detergentcomposition. For example, adjunct ingredients may be selected from thegroup consisting of nanoparticles, functionalized surface molecules,polymers, surfactants, co-surfactants, metal ions, proteins, dyes,acids, optical brighteners, colorants, filler salts, hydrotropes,preservatives, anti-oxidants, germicides, fungicides, color speckles,solubilizing agents, carriers and mixtures thereof.

Quite typically, cleaning compositions herein such as laundrydetergents, laundry detergent additives, hard surface cleaners,synthetic and soap-based laundry bars, fabric softeners and fabrictreatment liquids, solids and treatment articles of all kinds willrequire several adjuncts, though certain simply formulated products,such as bleach additives, may require only, for example, an oxygenbleaching agent and a surfactant as described herein. A comprehensivelist of suitable laundry or cleaning adjunct materials can be found inWO 99/05242.

Common cleaning adjuncts include builders, enzymes, polymers notdiscussed above, bleaches, bleach activators, catalytic materials andthe like excluding any materials already defined hereinabove. Othercleaning adjuncts herein can include suds boosters, suds suppressors(antifoams) and the like, diverse active ingredients or specializedmaterials such as dispersant polymers (e.g., from BASF Corp. or Rohm &Haas) other than those described above, color speckles, silvercare,anti-tarnish and/or anti-corrosion agents, dyes, fillers, germicides,alkalinity sources, hydrotropes, anti-oxidants, enzyme stabilizingagents, pro-perfumes, perfumes, solubilizing agents, carriers,processing aids, pigments, and, for liquid formulations, solvents,chelating agents, dye transfer inhibiting agents, dispersants,brighteners, suds suppressors, dyes, structure elasticizing agents,fabric softeners, anti-abrasion agents, hydrotropes, processing aids,and other fabric care agents, surface and skin care agents. Suitableexamples of such other cleaning adjuncts and levels of use are found inU.S. Pat. Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1.

The above-mentioned laundry detergent or cleaning composition preferablycontains cleaning adjunct additives selected from the group consistingof enzymes, alkali builders, chelant builders, bleaches, bleachingassisting agents, perfumes, defoaming agents, bactericides, corrosioninhibitors, and mixtures thereof.

Method of Use

The present invention includes a method for cleaning a targeted surface.As used herein “targeted surface” may include such surfaces such asfabric, dishes, glasses, and other cooking surfaces, hard surfaces, hairor skin. As used herein “hard surface” includes hard surfaces beingfound in a typical home such as hard wood, tile, ceramic, plastic,leather, metal, glass. Such method includes the steps of contacting thecomposition comprising the modified polyol compound, in neat form ordiluted in wash liquor, with at least a portion of a targeted surfacethen optionally rinsing the targeted surface. Preferably the targetedsurface is subjected to a washing step prior to the aforementionedoptional rinsing step. For purposes of the present invention, washingincludes, but is not limited to, scrubbing, wiping and mechanicalagitation.

As will be appreciated by one skilled in the art, the cleaningcompositions of the present invention are ideally suited for use in homecare (hard surface cleaning compositions) and/or laundry applications.

The composition solution pH is chosen to be the most complimentary to atarget surface to be cleaned spanning broad range of pH, from about 5 toabout 11. For personal care such as skin and hair cleaning pH of suchcomposition preferably has a pH from about 5 to about 8 for laundrycleaning compositions pH of from about 8 to about 10. The compositionsare preferably employed at concentrations of from about 200 ppm to about10,000 ppm in solution. The water temperatures preferably range fromabout 5° C. to about 100° C.

For use in laundry cleaning compositions, the compositions arepreferably employed at concentrations from about 200 ppm to about 10000ppm in solution (or wash liquor). The water temperatures preferablyrange from about 5° C. to about 60° C. The water to fabric ratio ispreferably from about 1:1 to about 20:1.

The method may include the step of contacting a nonwoven substrateimpregnated with an embodiment of the composition of the presentinvention As used herein “nonwoven substrate” can comprise anyconventionally fashioned nonwoven sheet or web having suitable basisweight, caliper (thickness), absorbency and strength characteristics.Examples of suitable commercially available nonwoven substrates includethose marketed under the tradename SONTARA® by DuPont and POLYWEB® byJames River Corp.

As will be appreciated by one skilled in the art, the cleaningcompositions of the present invention are ideally suited for use inliquid dish cleaning compositions. The method for using a liquid dishcomposition of the present invention comprises the steps of contactingsoiled dishes with an effective amount, typically from about 0.5 ml. toabout 20 ml. (per 25 dishes being treated) of the liquid dish cleaningcomposition of the present invention diluted in water.

If the above detergent compositions are liquid detergent compositions,the kaolin turbidity is generally below 200 mg/L, especially 150 mg/L,furthermore, 120 mg/L, preferably 100 mg/L and optimally 50 mg/L.

<Kaolin Turbidity Measurement Method>

A 10 mm thick and 50 mm square ell is filled with a sample (liquiddetergent) stirred thoroughly to form a homogeneous state, and afterdegassing, the turbidity (kaolin turbidity: mg/L) is measured at 25° C.with a Nippon Denshoku turbidity meter, Model NDH2000 (trade name:rabidity meter).

The above detergent composition shows an excellent ability inhibitingprecipitation, and it is possible to prepare a detergent compositionshowing extremely high quality performance and excellent stability beingless liable to form impurity precipitates in the case of low temperaturestorage and providing no performance reduction after long-term storage.

The present invention further contains a cleaning implement comprising anonwoven substrate and the above-mentioned laundry detergent or cleaningcomposition.

EXAMPLES

This invention is explained further in detail with application examplesas follows, but this invention is not necessarily limited to theseapplication examples alone. Incidentally, the “part” used is “part byweight” and “%” is “% by weight” unless specified.

Furthermore, the weight-average molecular weight, inhibitory ability,etc., of the hydrophobic group-containing copolymer of this inventionwere measure according the methods as follows.

<Weight-Average Molecular Weight Measurement Conditions>

Instrument: Hitachi L-7000 series

Detector: RI

Column: Showa Denko SHODEX Asahipak GF-310-HQ, GF-7, 10-HQ, GF-1G 7B

Column temperature: 40° C.

Flow rate: 0.5 mL/min

Working curve: Sowa Kagaku Polyacrylic acid standard

Elution solution: 0.1 N sodium acetate/acetonitrile=3/1 (ratio byweight)

<Method for Measurement of Precipitation Inhibitory Ability (AbilityInhibiting Precipitation of LAS-Ca Salt)>

(1) A glycine buffer solution was prepared by dissolving 9.3793 g ofglycine, 9.6452 g of sodium chloride and 5.1975 g of sodium hydroxide inpure water and making up to 1,000.0 g.

(2) To 1.50 g of a 15% (w/w) aqueous solution of sodiumdodecylbenzenesulfonate (LAS), 0.80 g of sodium sulfate and 11.25 g ofthe glycine buffer solution prepared in (1), pure water was added tomake up to 500.0 g.

(3) A 0.1% (w/w) aqueous solution of sample polymer was prepared.

(4) A 1 M aqueous solution of calcium chloride dihydrate was prepared.

(5) A 100 mL beaker was charged with 1.80 g of the 0.1% sample polymeraqueous solution prepared in (3), 8.20 g of pure water and 80.00 g ofthe solution mixture of (2) to obtain a test solution.

(6) To the test solution, the 1 M aqueous solution of calcium chloridedihydrate prepared in (4) was added in drops, the mixture was stirred,and the rabidity of the mixture was measured. For the measurement, aHiranuma Sanyo automated titrator (main unit: COM-550, opticalmeasurement unit: M-500). The turbidity changes were determined with thechanges in the transmittance at 650 nm wavelength.

(7) The transmittance at the point, where the amount of the 1 M aqueoussolution of calcium chloride dihydrate added was 0.270 mL, was set as aprecipitation inhibitory ability. Incidentally, the higher this value,the better the precipitation inhibitory ability.

<Polymer Composition Solid Content Measurement Method>

In an over at 130° C. under a nitrogen atmosphere, the polymercomposition (1.0 g of polymer composition+3.0 g of water) was allowed tostand for 1 h to carry out a drying treatment. From the weightdifference before and after drying, the solid content (%) and volatilecomponent (%) were calculated.

Monomer Synthetic Example 1

A 500 mL glass separable flask quipped with a stirrer (paddle blades)was charged with 81.2 g of New Cole 2305 (5 mol ethylene oxide adduct ofC₁₂₋₁₃ alcohol manufactured by Nippon Nyukazai K.K.) and 16.8 g ofpotassium hydroxide (“KOH” may be used below), nitrogen gas was blownin, the temperature was raised to 120° C. while stirring, and the samestate was maintained for 1 h to carry out dehydration of the reactionsystem. A reflux condenser was attached, the temperature was reduceddown to 60° C., 27.0 g of methallyl chloride (called MLC, below) wasadded taking 30 min, and subsequently, the reaction was carried out for5 h. Subsequently, 200.0 g of pure water was added, the mixture wastransferred to a separation funnel, allowed to stand for separation, andthe bottom layer was removed. Subsequently, the top layer wastransferred to a 300 mL pear flask, and the solvent was removed with arotary evaporator. The salt precipitated was removed with filtration toobtain a monomer 1.

Application Example 1

A 1000 mL separable flask equipped with a reflux condenser, stirrer(paddle blades) was charged with 73.0 g of pure water, and 0.0127 g ofMohr's salt, and the temperature was raised to 90° C. while stirring toprepare a polymerization reaction system, While stirring thepolymerization reaction system maintained at 90° C., 237.5 g of an 80%aqueous solution of acrylic acid (called 80% AA, below), 11.0 g of a 48%aqueous solution of sodium hydroxide (called 48% NaOH, below), 10.0 g ofa monomer 1, 53.2 g of a 15% aqueous solution of sodium persulfate(called 15% NaPS, below) and 30.4 g of a 35% aqueous solution of sodiumhydrogen sulfite (called 35% SBS, below) were added in drops fromseparate respective nozzles. The dropping times for the respectivesolutions were 180 min for the 80% AA and 48% NaOH, 120 min for themonomer 1, 190 min for the 15% NaPS and 175 min for the 35% SBS. Thespeed of the addition of the respective solutions was set constant, andthe addition was carried out continuously.

After completing the addition of the 80% AA, the reaction mixturesolution was maintained (aged) at 90° C. for 30 min to complete thepolymerization reaction. After completing the polymerization reaction,the reaction mixture solution was cooled while stirring, and 186.9 g ofthe 48% NaOH was added gradually in drops to neutralize thepolymerization reaction mixture solution.

As a result, it was possible to prepare an aqueous solution of thepolymer 1 with a solid content of 44.8% and weight-average molecularweight of 8500 (polymer composition 1 of this invention).

Application Example 2

A 1000 mL separable flask equipped with a reflux condenser, stirrer(paddle blades) was charged with 89.0 g of pure water, 30.0 g of themonomer 1 and 0.0126 g of Mohr's salt, and the temperature was raised to90° C. while stirring to prepare a polymerization reaction system, Whilestirring the polymerization reaction system maintained at 90° C., 212.5g of the 80% AA, 9.8 g of the 48% NaOH, 48.5 g of the 15% NaPS and 34.7of the 35% SBS were added in drops from separate respective nozzles. Thedropping times for the respective solutions were 180 min for the 80% AAand 48% NaOH, 190 min for the 15% NaPS and 175 min for the 35% SBS. Thespeed of the addition of the respective solutions was set constant, andthe addition was carried out continuously.

After completing the addition of the 80% AA, the reaction mixturesolution was maintained (aged) at 90° C. for 30 min to complete thepolymerization reaction. After completing the polymerization reaction,the reaction mixture solution was cooled while stirring, and 167.2 g ofthe 48% NaOH was added gradually in drops to neutralize thepolymerization reaction mixture solution.

As a result, it was possible to prepare an aqueous solution of thepolymer 2 with a solid content of 45.0% and weight-average molecularweight of 9700 (polymer composition 2 of this invention).

Monomer Synthetic Example 2

A 500 mL glass separable flask quipped with a stirrer (paddle blades)and reflux condenser was charged with 370.0 g of n-butyl alcohol and4.27 g of KOH, the temperature was raised to 90° C. while stirring.Subsequently, 57.0 g of allyl glycidyl ether (also called AGE, below)was added by taking 30 min, and subsequently, the reaction was carriedout for 5 h. After cooling to room temperature, the reaction mixturesolution was neutralized with sulfuric acid, transferred to a 1000 mLpear-shaped flask, and the solvent removal was carried out with a rotaryevaporator. Subsequently, 200.0 g of pure water was added, the mixturewas transferred to a 500 mL separation funnel, allowed to stand forseparation, and the bottom layer was removed. Subsequently, the toplayer was transferred to a 300 mL pear flask, and the solvent wasremoved with a rotary evaporator. The salt precipitate was removed withfiltration to obtain a monomer 2.

Application Example 3

A 1000 mL glass separable flask equipped with a reflux condenser,stirrer (paddle blades) was charged with 77.0 g of pure water and 0.0128g of Mohr's salt, and the temperature was raised to 90° C. whilestirring to prepare a polymerization reaction system, While stirring thepolymerization reaction system maintained at 90° C., 225.0 g of the 80%AA, 10.4 g of the 48% NaOH, 20.0 g of the monomer 2, 52.1 g of the 15%NaPS and 44.7 of the 35% SBS were added in drops from separaterespective nozzles. The dropping times for the respective solutions were180 min for the 80% AA and 48% NaOH, 120 min for the monomer 2, 190 minfor the 15% NaPS and 175 min for the 35% SBS. The speed of the additionof the respective solutions was set constant, and the addition wascarried out continuously.

After completing the addition of the 80% AA, the reaction mixturesolution was maintained (aged) at 90° C. for 30 min to complete thepolymerization reaction. After completing the polymerization reaction,the reaction mixture solution was cooled while stirring, and 177.1 g ofthe 48% NaOH was added gradually in drops to neutralize thepolymerization reaction mixture solution.

As a result, it was possible to prepare an aqueous solution of thepolymer 3 with a solid content of 44.9% and weight-average molecularweight of 9200 (polymer composition 3 of this invention).

Monomer Synthetic Example 3

A 500 mL glass separable flask quipped with a stirrer (paddle blades)and reflux condenser was charged with 34.8 g 1 mol ethylene oxide adductof methacrylic alcohol (also called MLA, below) and 1.8 g of KOH, thetemperature was raised to 90° C. while stirring. Subsequently, 55.8 g of2-ethylhexyl glycidyl ether (also called EHGE, below) was added bytaking 30 min, and subsequently, the reaction was carried out for 5 h.Subsequently, 200.0 g of pure water was added, and after carrying outthe reaction for 1 h, the reaction mixture was neutralized with sulfuricacid. After cooling to room temperature, the reaction mixture solutionwas transferred to a 500 mL separation funnel, allowed to stand forseparation, and the bottom layer was removed. Subsequently, the toplayer was transferred to a 300 mL pear flask, and the solvent wasremoved with a rotary evaporator. The salt precipitate was removed withfiltration to obtain a monomer 3.

Application Example 4

A 1000 mL glass separable flask equipped with a reflux condenser,stirrer (paddle blades) was charged with 85.0 g of pure water and 0.0127g of Mohr's salt, and the temperature was raised to 90° C. whilestirring to prepare a polymerization reaction system, While stirring thepolymerization reaction system maintained at 90° C., 212.5 g of the 80%AA, 9.8 g of the 48% NaOH, 30.0 g of the monomer 3, 49.2 g of the 15%NaPS and 49.2 of the 35% SBS were added in drops from separaterespective nozzles. The dropping times for the respective solutions were180 min for the 80% AA and 48% NaOH, 120 min for the monomer 3, 190 minfor the 15% NaPS and 175 min for the 35% SBS. The speed of the additionof the respective solutions was set constant, and the addition wascarried out continuously.

After completing the addition of the 80% AA, the reaction mixturesolution was maintained (aged) at 90° C. for 30 min to complete thepolymerization reaction. After completing the polymerization reaction,the reaction mixture solution was cooled while stirring, and 167.2 g ofthe 48% NaOH was added gradually in drops to neutralize thepolymerization reaction mixture solution.

As a result, it was possible to prepare an aqueous solution of thepolymer 4 with a solid content of 44.8% and weight-average molecularweight of 7600 (polymer composition 4 of this invention).

Monomer Synthetic Example 4

A 500 mL glass separable flask quipped with a stirrer (paddle blades)and reflux condenser was charged with 46.4 g of MLA1 and 2.0 g of KOH,the temperature was raised to 90° C. while stirring. Subsequently, 52.0g of n-butyl glycidyl ether (also called BGE, below) was added by taking30 min, and subsequently, the reaction was carried out for 5 h.Subsequently, 200.0 g of pure water was added, and after carrying outthe reaction for 1 h, the reaction mixture was neutralized with sulfuricacid. After cooling to room temperature, the reaction mixture solutionwas transferred to a 500 mL separation funnel, allowed to stand forseparation, and the bottom layer was removed. Subsequently, the toplayer was transferred to a 300 mL pear flask, and the solvent wasremoved with a rotary evaporator. The salt precipitate was removed withfiltration to obtain a monomer 4.

Application Example 5

A 1000 mL separable flask equipped with a reflux condenser, stirrer(paddle blades) was charged with 95.0 g of pure water, 40.0 g of themonomer 4 and 0.0124 g of Mohr's salt, and the temperature was raised to90° C. while stirring to prepare a polymerization reaction system, Whilestirring the polymerization reaction system maintained at 90° C., 200.0g of the 80% AA, 9.3 g of the 48% NaOH, 47.7 g of the 15% NaPS and 40.9g of the 35% SBS were added in drops from separate respective nozzles.The dropping times for the respective solutions were 180 min for the 80%AA and 48% NaOH, 185 min for the 15% NaPS and 175 min for the 35% SBS.The speed of the addition of the respective solutions was set constant,and the addition was carried out continuously.

After completing the addition of the 80% AA, the reaction mixturesolution was maintained (aged) at 90° C. for 30 min to complete thepolymerization reaction. After completing the polymerization reaction,the reaction mixture solution was cooled while stirring, and 157.4 g ofthe 48% NaOH was added gradually in drops to neutralize thepolymerization reaction mixture solution.

As a result, it was possible to prepare an aqueous solution of thepolymer 5 with a solid content of 44.8% and weight-average molecularweight of 9000 (polymer composition 5 of this invention).

Monomer Synthetic Example 5

A 500 mL glass separable flask quipped with a stirrer (paddle blades)was charged with 63.6 g of New Cole 2303 (3 mol ethylene oxide adduct ofC₁₂₋₁₃ alcohol manufactured by Nippon Nyukazai K.K.) and 16.8 g of KOH,nitrogen gas was blown in, the temperature was raised to 120° C. whilestirring, and the same state was maintained for 1 h to carry outdehydration of the reaction system. A reflux condenser was attached, thetemperature was reduced down to 60° C., 27.0 g of MLC was added taking30 min, and subsequently, the reaction was carried out for 5 h.Subsequently, 200.0 g of pure water was added, and after carrying outthe reaction for 1 h, the reaction mixture was neutralized with sulfuricacid. After cooling to room temperature, the reaction mixture solutionwas transferred to a 500 mL separation funnel, allowed to stand forseparation, and the bottom layer was removed. Subsequently, the toplayer was transferred to a 300 mL pear flask, and the solvent wasremoved with a rotary evaporator. The salt precipitate was removed withfiltration to obtain a monomer 5.

Application Example 6

A 1000 mL glass separable flask equipped with a reflux condenser,stirrer (paddle blades) was charged with 70.0 g of pure water and 0.0130g of Mohr's salt, and the temperature was raised to 90° C. whilestirring to prepare a polymerization reaction system, While stirring thepolymerization reaction system maintained at 90° C., 237.5 g of the 80%AA, 11.0 g of the 48% NaOH, 10.0 g of the monomer 5, 53.2 g of the 15%NaPS and 45.6 g of the 35% SBS were added in drops from separaterespective nozzles. The dropping times for the respective solutions were180 min for the 80% AA and 48% NaOH, 120 min for the monomer 5, 185 minfor the 15% NaPS and 175 min for the 35% SBS. The speed of the additionof the respective solutions was set constant, and the addition wascarried out continuously.

After completing the addition of the 80% AA, the reaction mixturesolution was maintained (aged) at 90° C. for 30 min to complete thepolymerization reaction. After completing the polymerization reaction,the reaction mixture solution was cooled while stirring, and 186.9 g ofthe 48% NaOH was added gradually in drops to neutralize thepolymerization reaction mixture solution.

As a result, it was possible to prepare an aqueous solution of thepolymer 6 with a solid content of 45.2% and weight-average molecularweight of 7500 (polymer composition 6 of this invention).

Monomer Synthetic Example 6

A 500 mL glass separable flask quipped with a stirrer (paddle blades)was charged with 61.2 g of New Cole 1004 (4 mol ethylene oxide adduct ofC₁₂₋₁₃ alcohol manufactured by Nippon Nyukazai K.K.) and 16.8 g of KOH,nitrogen gas was blown in, the temperature was raised to 120° C. whilestirring, and the same state was maintained for 1 h to carry outdehydration of the reaction system. A reflux condenser was attached, thetemperature was reduced down to 60° C., 27.0 g of MLC was added taking30 min, and subsequently, the reaction was carried out for 5 h.Subsequently, 200.0 g of pure water was added, and after carrying outthe reaction for 1 h, the reaction mixture was neutralized with sulfuricacid. After cooling to room temperature, the reaction mixture solutionwas transferred to a 500 mL separation funnel, allowed to stand forseparation, and the bottom layer was removed. Subsequently, the toplayer was transferred to a 300 mL pear flask, and the solvent wasremoved with a rotary evaporator. The salt precipitate was removed withfiltration to obtain a monomer 6.

Application Example 7

A 1000 mL glass separable flask equipped with a reflux condenser,stirrer (paddle blades) was charged with 110.0 g of pure water and0.0122 g of Mohr's salt, and the temperature was raised to 90° C. whilestirring to prepare a polymerization reaction system. While stirring thepolymerization reaction system maintained at 90° C., 175.0 g of the 80%AA, 8.1 g of the 48% NaOH, 60.0 g of the monomer 6, 42.0 g of the 15%NaPS and 48.0 of the 35% SBS were added in drops from separaterespective nozzles. The dropping times for the respective solutions were180 min for the 80% AA and 48% NaOH, 120 min for the monomer 6, 185 minfor the 15% NaPS and 175 min for the 35% SBS. The speed of the additionof the respective solutions was set constant, and the addition wascarried out continuously.

After completing the addition of the 80% AA, the reaction mixturesolution was maintained (aged) at 90° C. for 30 min to complete thepolymerization reaction. After completing the polymerization reaction,the reaction mixture solution was cooled while stirring, and 137.7 g ofthe 48% NaOH was added gradually in drops to neutralize thepolymerization reaction mixture solution.

As a result, it was possible to prepare an aqueous solution of thepolymer 7 with a solid content of 45.0% and weight-average molecularweight of 8900 (polymer composition 7 of this invention).

Application Example 8

A 1000 mL glass separable flask equipped with a reflux condenser,stirrer (paddle blades) was charged with 82.0 g of pure water and 8.0 gof the monomer 1, and the temperature was raised to 90° C. whilestirring to prepare a polymerization reaction system. While stirring thepolymerization reaction system maintained at 90° C., 90.0 g of the 80%AA and 32.3 g of the 15% NaPS were added in drops from separaterespective nozzles. The dropping times for the respective solutions were90 min for the 80% AA and 110 min for the 15% NaPS. The speed of theaddition of the respective solutions was set constant, and the additionwas carried out continuously.

After completing the addition of the 80% AA, the reaction mixturesolution was maintained (aged) at 90° C. for 60 min to complete thepolymerization reaction. After completing the polymerization reaction,the reaction mixture solution was cooled while stirring, and 70.8 g ofthe 48% NaOH and 8.0 g of pure water were added gradually in drops toneutralize and dilute the polymerization reaction mixture solution.

As a result, it was possible to prepare an aqueous solution of thepolymer 8 with a solid content of 36.0% and weight-average molecularweight of 112000 (polymer composition 8 of this invention).

Comparative Example 1

A 1000 mL glass separable flask equipped with a reflux condenser,stirrer (paddle blades) was charged with 119.0 g of pure water and0.0120 g of Mohr's salt, and the temperature was raised to 90° C. whilestirring to prepare a polymerization reaction system. While stirring thepolymerization reaction system maintained at 90° C., 175.0 g of the 80%AA, 8.1 g of the 48% NaOH, 60.0 g of styrene (also called St, below),33.6 g of the 15% NaPS and 36.0 g of the 35% SBS were added in dropsfrom separate respective nozzles. The dropping times for the respectivesolutions were 180 min for the 80% AA and 48% NaOH, 120 min for St, 185min for the 15% NaPS and 175 min for the 35% SBS. The speed of theaddition of the respective solutions was set constant, and the additionwas carried out continuously.

After completing the addition of the 80% AA, the reaction mixturesolution was maintained (aged) at 90° C. for 30 min to complete thepolymerization reaction. After completing the polymerization reaction,the reaction mixture solution was cooled while stirring, and 137.7 g ofthe 48% NaOH was added gradually in drops to neutralize thepolymerization reaction mixture solution.

As a result, it was possible to prepare an aqueous solution of thecomparative polymer 1 with a solid content of 45.0% and weight-averagemolecular weight of 8600 (comparative polymer composition 1 of thisinvention).

Comparative Example 2

A 1000 mL glass separable flask equipped with a reflux condenser,stirrer (paddle blades) was charged with 119.0 g of pure water and0.0120 g of Mohr's salt, and the temperature was raised to 90° C. whilestirring to prepare a polymerization reaction system. While stirring thepolymerization reaction system maintained at 90° C., 175.0 g of the 80%AA, 8.1 g of the 48% NaOH, 60.0 g of butyl acrylate (also called BA,below), 32.7 g of the 15% NaPS and 35.0 g of the 35% SBS were added indrops from separate respective nozzles. The dropping times for therespective solutions were 180 min for the 80% AA and 48% NaOH, 120 minfor BA, 185 min for the 15% NaPS and 175 min for the 35% SBS. The speedof the addition of the respective solutions was set constant, and theaddition was carried out continuously.

After completing the addition of the 80% AA, the reaction mixturesolution was maintained (aged) at 90° C. for 30 min to complete thepolymerization reaction. After completing the polymerization reaction,the reaction mixture solution was cooled while stirring, and 137.7 g ofthe 48% NaOH was added gradually in drops to neutralize thepolymerization reaction mixture solution.

As a result, it was possible to prepare an aqueous solution of thecomparative polymer 2 with a solid content of 44.6% and weight-averagemolecular weight of 7200 (comparative polymer composition 2 of thisinvention).

Application Example 9

The precipitation inhibitory ability was evaluated for the polymercompositions of the application examples 1-7 and comparative examples1-2 with the evaluation method described above. The results obtained aresummarized in Table 1.

TABLE 1 Ether bond-containing No. of carbon monomer-origin structural inthe unit/carboxyl group- Solid Molecular Precipitation hydrophobiccontaining monomer- content weight inhibitory group origin structuralunit (%) (Mw/Mn) ability Application Example 1 12  5/95 44.8 8500/300081 Application Example 2 12 15/85 45   9700/3600 79 Application Example3 4 10/90 44.9 9200/3400 75 Application Example 4 8 15/85 44.8 7600/280078 Application Example 5 4 20/80 44.8 9000/3500 78 Application Example 612  5/95 45.2 7500/2500 82 Application Example 7 8 30/70 45   8900/320082 Comparative Example 1 6 None (except St 10)/90 45   8600/3000 62Comparative Example 2 4 None (except BA 10)/90 44.6 7200/3200 68

As apparent from the results shown in Table 1, the polymer compositionof this invention was found to have a significantly excellentprecipitation inhibitory ability compared with the comparative polymercompositions containing comparative polymers having no structural unitoriginated from ether bond-containing monomers as a hydrophobic monomer

Composition Formulations Granular Laundry Detergent Examples 10

A B C D E Formula wt % wt % wt % wt % wt % C₁₁₋₁₂ Linear alkyl benzene13-25 13-25 13-25 13-25  9-25 sulphonate C₁₂₋₁₈ Ethoxylate Sulfate — —0-3 — 0-1 C₁₄₋₁₅ alkyl ethoxylate (EO = 7) 0-3 0-3 — 0-5 0-3 Dimethylhydroxyethyl lauryl — — 0-2 0-2 0-2 ammonium chloride

Sodium tripolyphosphate K1 20-40 — 18-33 12-22  0-15 Zeolite  0-10 20-400-3 — — Silicate builder  0-10  0-10  0-10  0-10  0-10 Carbonate  0-30 0-30  0-30  5-25  0-20 Diethylene triamine penta 0-1 0-1 0-1 0-1 0-1acetate Polyacrylate 0-3 0-3 0-3 0-3 0-3 Carboxy Methyl Cellulose0.2-0.8 0.2-0.8 0.2-0.8 0.2-0.8 0.2-0.8 Copolymer¹  1-20  1-20 5.0 102.5 Percarbonate  0-10  0-10  0-10  0-10  0-10Nonanoyloxybenzenesulfonate — — 0-2 0-2 0-2 Tetraacetylethylenediamine ——   0-0.6   0-0.6   0-0.6 Zinc Phthalocyanine — —     0-0.005    0-0.005     0-0.005 Tetrasulfonate Brightener 0.05-0.2  0.05-0.2 0.05-0.2  0.05-0.2  0.05-0.2  MgSO₄ — —   0-0.5   0-0.5   0-0.5 Enzymes  0-0.5   0-0.5   0-0.5   0-0.5   0-0.5 Minors (perfume, dyes, sudsbalance balance balance balance balance stabilizers) ¹A copolymeraccording to any of Application Examples 1, 2, 3, 4, 5, 6, 7 or 8.

Granular Laundry Detergent Example 11 Aqueous Slurry Composition

% w/w Aqueous Component slurry A compound having the following generalstructure: 1.23 bis((C₂H₅O)(C₂H₄O)n)(CH₃)—N⁺³⁰—C_(x)H_(2x)—N⁺—(CH₃)—bis((C₂H₅O)(C₂H₄O)n), wherein n = from 20 to 30, and x = from 3 to 8, orsulphated or sulphonated variants thereof Ethylenediamine disuccinicacid 0.35 Brightener 0.12 Magnesium sulphate 0.72 Acrylate/maleatecopolymer 6.45 Copolymer ¹ 1.60 Linear alkyl benzene sulphonate 11.92Hydroxyethane di(methylene phosphonic acid) 0.32 Sodium carbonate 4.32Sodium sulphate 47.49 Soap 0.78 Water 24.29 Miscellaneous 0.42 TotalParts 100.00 ¹ A copolymer or any mixture of copolymers according to anyof Application Examples 1, 2, 3, 4, 5, 6, 7 or 8.Preparation of a Spray-Dried Powder.

An aqueous slurry having the composition as described above is preparedhaving a moisture content of 25.89%. The aqueous slurry is heated to 72°C. and pumped under high pressure (from 5.5×10⁶Nm⁻² to 6.0×10⁶Nm⁻²),into a counter current spray-drying tower with an air inlet temperatureof from 270° C. to 300° C. The aqueous slurry is atomised and theatomised slurry is dried to produce a solid mixture, which is thencooled and sieved to remove oversize material (>1.8 mm) to form aspray-dried powder, which is free-flowing. Fine material (<0.15 mm) iselutriated with the exhaust the exhaust air in the spray-drying towerand collected in a post tower containment system. The spray-dried powderhas a moisture content of 1.0 wt %, a bulk density of 427 g/l and aparticle size distribution such that 95.2 wt % of the spray-dried powderhas a particle size of from 150 to 710 micrometers. The composition ofthe spray-dried powder is given below.

Spray-Dried Powder Composition.

% w/w Spray- Component dried powder A compound having the followinggeneral structure: 1.62bis((C₂H₅O)(C₂H₄O)n)(CH₃)-N⁺—C_(x)H_(2x)—N⁺—(CH₃)— bis((C₂H₅O)(C₂H₄O)n),wherein n = from 20 to 30, and x = from 3 to 8, or sulphated orsulphonated variants thereof Ethylenediamine disuccinic acid 0.46Brightener 0.16 Magnesium sulphate 0.95 Acrylate/maleate copolymer 8.45Copolymer¹ 2.09 Linear alkyl benzene sulphonate 15.65 Hydroxyethanedi(methylene phosphoric acid) 0.42 Sodium carbonate 5.65 Sodium sulphate61.98 Soap 1.02 Water 1.00 Miscellaneous 0.55 Total Parts 100.00 ¹Acopolymer or any mixture of copolymers according to any of ApplicationExamples 1, 2, 3, 4, 5, 6, 7 or 8.Preparation of an Anionic Surfactant Particle 1

The anionic detersive surfactant particle 1 is made on a 520 g batchbasis using a Tilt-A-Pin then Tilt-A-Plow mixer (both made byProcessall). 108 g sodium sulphate supplied is added to the Tilt-A-Pinmixer along with 244 g sodium carbonate. 168 g of 70% active C₂₅E₃Spaste (sodium ethoxy sulphate based on C_(12/15) alcohol and ethyleneoxide) is added to the Tilt-A-Pin mixer. The components are then mixedat 1200 rpm for 10 seconds. The resulting powder is then transferredinto a Tilt-A-Plow mixer and mixed at 200 rpm for 2 minutes to formparticles. The particles are then dried in a fluid bed dryer at a rateof 25001/min at 120° C. until the equilibrium relative humidity of theparticles is less than 15%. The dried particles are then sieved and thefraction through 1180 μm and on 250 μm is retained The composition ofthe anionic detersive surfactant particle 1 is as follows:

25.0% w/w C₂₅E₃S sodium ethoxy sulphate

18.0% w/w sodium sulphate

57.0% w/w sodium carbonate

Preparation of a Cationic Detersive Surfactant Particle 1

The cationic surfactant particle 1 is made on a 14.6 kg batch basis on aMorton FM-50 Loedige mixer. 4.5 kg of micronised sodium sulphate and 4.5kg micronised sodium carbonate are premixed in the Morton FM-50 Loedigemixer. 4.6 kg of 40% active mono-C₁₂₋₁₄ alkyl mono-hydroxyethyldi-methyl quaternary ammonium chloride (cationic surfactant) aqueoussolution is added to the Morton FM-50 Loedige mixer whilst both the maindrive and the chopper are operating. After approximately two minutes ofmixing, a 1.0 kg 1:1 weight ratio mix of micronised sodium sulphate andmicronised sodium carbonate is added to the mixer. The resultingagglomerate is collected and dried using a fluid bed dryer on a basis of25001/min air at 100-140° C. for 30 minutes. The resulting powder issieved and the fraction through 1400 μm is collected as the cationicsurfactant particle 1. The composition of the cationic surfactantparticle 1 is as follows:

15% w/w mono-C₁₂₋₁₄ alkyl mono-hydroxyethyl di-methyl quaternaryammonium chloride

40.76% w/w sodium carbonate

40.76% w/w sodium sulphate

3.48% w/w moisture and miscellaneous

Preparation of a Granular Laundry Detergent Composition

10.84 kg of the spray-dried powder of example 6, 4.76 kg of the anionicdetersive surfactant particle 1, 1.57 kg of the cationic detersivesurfactant particle 1 and 7.83 kg (total amount) of other individuallydosed dry-added material are dosed into a 1 m diameter concrete batchmixer operating at 24 rpm. Once all of the materials are dosed into themixer, the mixture is mixed for 5 minutes to form a granular laundrydetergent composition. The formulation of the granular laundry detergentcomposition is described below:

A Granular Laundry Detergent Composition.

% w/w granular laundry detergent compo- Component sition Spray-driedpowder from earlier table in Example 5 43.34 91.6 wt % active linearalkyl benzene sulphonate 0.22 flake supplied by Stepan under thetradename Nacconol 90G ® Citric acid 5.00 Sodium percarbonate 14.70(having from 12% to 15% active AvOx) Photobleach particle 0.01 Lipase(11.00 mg active/g) 0.70 Amylase (21.55 mg active/g) 0.33 Protease(56.00 mg active/g) 0.43 Tetraacetyl ethylene diamine agglomerate (92 wt% active) 4.35 Suds suppressor agglomerate (11.5 wt % active) 0.87Acrylate/maleate copolymer particle (95.7 wt % active) 0.29 Green/Bluecarbonate speckle 0.50 Anionic detersive surfactant particle 1 19.04Cationic detersive surfactant particle 1 6.27 Sodium sulphate 3.32 Solidperfume particle 0.63 Total Parts 100.00

Liquid Laundry Detergents Example 12

A B C D E Ingredient wt % wt % wt % wt % wt % Sodium alkyl  14.4%  9.2% 5.4% ether sulfate Linear   4.4%  12.2%  5.7%  1.3% alkylbenzenesulfonic acid Alkyl   2.2%  8.8%  8.1%  3.4% ethoxylate Amine oxide  0.7%  1.5% Citric acid   2.0%  3.4%  1.9%  1.0%  1.6% Fatty acid  3.0%  8.3%  16.0% Protease   1.0%  0.7%  1.0%  2.5% Amylase   0.2% 0.2%  0.3% Borax   1.5%  2.4%  2.9% Calcium   0.2% and sodium formateFormic acid  1.1% Copolymer¹   1.8%  2.1%  3.2% Sodium  0.2%polyacrylate Sodium  0.6% polyacrylate copolymer Fluorescent  0.15% 0.2%  0.12%  0.12%  0.2% whitening agent Ethanol   2.5%  1.4%  1.5%Propanediol   6.6%  4.9%  4.0%  15.7% Sorbitol  4.0% Ethanolamine   1.5% 0.8%  0.1%  11.0% Sodium   3.0%  4.9%  1.9%  1.0% hydroxide Sodium 2.0% cumene sulfonate Silicone suds  0.01% suppressor Perfume   0.3% 0.7%  0.3%  0.4%  0.6% Opacifier⁵  0.30%  0.20%  0.50% Water balancebalance balance balance balance 100.0% 100.0% 100.0% 100.0% 100.0% ¹Acopolymer or any mixture of copolymers according to any of ApplicationExamples 1, 2, 3, 4, 5, 6, 7 or 8. ²diethylenetriaminepentaacetic acid,sodium salt ³diethylenetriaminepentakismethylenephosphonic acid, sodiumsalt ⁴ethylenediaminetetraacetic acid, sodium salt ⁵Acusol OP 301

F G H I J K Ingredient wt % wt % wt % wt % wt % wt % Alkylbenzenesulfonic acid 7 7 4.5 1.2 1.5 12.5 Sodium C12-14 alkyl ethoxy 3 2.3 2.34.5 4.5 7 18 sulfate C14-15 alkyl 8-ethoxylate 5 5 2.5 2.6 4.5 4 C12alkyl dimethyl amine oxide — 2 — — — — C12-14 alkyl hydroxyethyl — — —0.5 — — dimethyl ammonium chloride C12-18 Fatty acid 2.6 3 4 2.6 2.8 11Citric acid 2.6 2 1.5 2 2.5 3.5 Protease enzyme 0.5 0.5 0.6 0.3 0.5 2Amylase enzyme 0.1 0.1 0.15 — 0.05 0.5 Mannanase enzyme 0.05 — 0.05 — —0.1 Copolymer¹ 1.0 .8 1 0.4 1.5 2.7 Hydroxyethane diphosphonic — — 0.45— — 1.5 acid FWA 0.1 0.1 0.1 — — 0.2 Solvents (1,2 propanediol, 3 4 1.51.5 2 4.3 ethanol), stabilizers Hydrogenated castor oil 0.4 0.3 0.3 0.10.3 — derivative structurant Boric acid 1.5 2 2 1.5 1.5 0.5 Na formate —— — 1 — — Reversible protease inhibitor³ — — 0.002 — — — Perfume 0.5 0.70.5 0.5 0.8 1.5 Buffers (sodium hydroxide, To pH 8.2 Monoethanolamine)Water and minors (antifoam, To 100 aesthetics, . . .) ¹The copolymer orany mixture of copolymers according to any of Application Examples 1, 2,3, 4, 5, 6, 7 or 8.

L M N O P Q Ingredient wt % wt % wt % wt % wt % wt % Alkylbenzenesulfonic acid 5.5 2.7 2.2 12.2 5.2 5.2 Sodium C12-14 alkyl ethoxy 16.520 9.5 7.7 1.8 1.8 3 sulfate Sodium C12-14 alkyl sulfate 8.9 6.5 2.9 —C12-14 alkyl 7-ethoxylate 0.15 0.15 C14-15 alkyl 8-ethoxylate 3.5 3.5C12-15 alkyl 9-ethoxylate 1.7 0.8 0.3 18.1 — — C12-18 Fatty acid 2.2 2.0— 1.3 2.6 2.6 Citric acid 3.5 3.8 2.2 2.4 2.5 2.5 Protease enzyme 1.71.4 0.4 — 0.5 0.5 Amylase enzyme 0.4 0.3 — — 0.1 0.1 Mannanase enzyme0.04 0.04 Copolymer¹ 2.1 1.2 1.0 2 1.00 0.25 PEG-PVAc Polymer² — — — — —0.3 Ethoxysulfated — — — — — 0.7 Hexamethylene Diamine — — — — — —Dimethyl Quat — — — — — — FWA — — — — .04 .04 Solvents (1,2 propanediol,7 7.2 3.6 3.7 1.9 1.9 ethanol, stabilizers Hydrogenated castor oil 0.30.2 0.2 0.2 0.35 0.35 derivative structurant Polyacrylate — — — 0.1 — —Polyacrylate copolymer³ — — — 0.5 — — Sodium carbonate — — — 0.3 — —Sodium silicate — — — — — — Borax 3 3 2 1.3 — — Boric acid 1.5 2 2 1.51.5 1.5 Perfume 0.5 0.5 0.5 0.8 0.5 0.5 Buffers (sodium hydroxide, 3.33.3 monoethanolamine) Water, dyes and miscellaneous Balance ¹Copolymeror any mixture of copolymers according to any of Application Examples 1,2, 3, 4, 5, 6, 7 or 8. ²PEG-PVA graft copolymer is a polyvinyl acetategrafted polyethylene oxide copolymer having a polyethylene oxidebackbone and multiple polyvinyl acetate side chains. The molecularweight of the polyethylene oxide backbone is about 6000 and the weightratio of the polyethylene oxide to polyvinyl acetate is about 40 to 60and no more than 1 grafting point per 50 ethylene oxide units. ³Alco 725(styrene/acrylate)

Liquid Dish Handwashing Detergents Example 13

Composition A B C₁₂₋₁₃ Natural AE0.6S 29.0 29.0 C₁₀₋₁₄ mid-branchedAmine Oxide — 6.0 C₁₂₋₁₄ Linear Amine Oxide 6.0 — SAFOL ® 23 Amine Oxide1.0 1.0 C₁₁E₉ Nonionic² 2.0 2.0 Ethanol 4.5 4.5 Copolymer¹ 5.0 2.0Sodium cumene sulfonate 1.6 1.6 Polypropylene glycol 2000 0.8 0.8 NaCl0.8 0.8 1,3 BAC Diamine³ 0.5 0.5 Suds boosting polymer⁴ 0.2 0.2 WaterBalance Balance ¹A copolymer or any mixture of polymers according to anyof Application Examples 1, 2, 3, 4, 5, 6, 7 or 8. ²Nonionic may beeither C₁₁ Alkyl ethoxylated surfactant containing 9 ethoxy groups.³1,3,BAC is 1,3 bis(methylamine)-cyclohexane. ⁴(N,N-dimethylamino)ethylmethacrylate homopolymer

Automatic Dishwasher Detergents Example 14

A B C D E F G Sodium 0 6 10 0-20 0 0 0 tripolyphosphate Silicate solids6 6 6 6-10 1.5-2.5 2.5-6 2.5-6 Carbonate 35 40 40 25-40 25-40 25-40Sodium 5-15 Bicarbonate Xanthan gum 0.5-1.0 MGDA 4.0-7.5 4-7 2-4 HEDP0.05-0.3 0.05-0.3 Nonionic 0 0 0 0.5-5 0.5-5 0.5-1.0 0.5-1.0 surfactant¹Polymer 0.5 5 6 5 0.1-2.0 0.1-2.0 dispersant² Polymer 0.5-3.0dispersant³ Copolymer⁴ 0.05-10 1 2.5 5 6-8 4-6 2-3 Enzymes 0.3-0.80.3-0.8 0.3-0.8 0.3-0.8 0.5-1.0 0.25-0.6 0.25-0.6 Bleach and 4 4 4 4 02.0-4.0 2.0-4.0 bleach activators Disodium citrate 0 0 0 2-20 0 0 0dihydrate Sodium Sulfate 30-50 30-50 30-50 30-50 0 30-50 30-50 Perfume0.01-0.1 0.01-0.1 0.01-0.1 0.01-0.1 0.01-0.1 0.01-0.1 0.01-0.1 Water,dye and other Balance Balance Balance Balance Balance Balance Balanceadjuncts to 100% to 100% to 100% to 100% to 100% to 100% to 100% ¹Suchas SLF-18 POLY TERGENT from the BASF Corporation. ²Copolymer such asACUSOL ® 445N from Rohm & Haas or ALCOSPERSE ® 725 from Alco.³Ethoxylated cationic diame such as those disclosed in U.S. Pat. No.4,659,802. ⁴A copolymer or any mixture of copolymers according to any ofApplication Examples 1, 2, 3, 4, 5, 6, 7 or 8.

Automatic Dishwashing Unit-Dose Products Example 15

Example A Particulate composition STPP 0 Silicate 2-8 Carbonate 25-50Copolymer¹  5-10 Polymer Dispersant² 1-5 Nonionic Surfactant³ 1-5 Enzyme1-6 Bleach and Bleach 2.5-10  Activators Perfume 0.05-1   Sodium Sulfate 0-10 Liquid composition DPG 40-50 Nonionic Surfactant³ 40-50 NeodolC11E9   0-5.0 Glycerine   0-5.0 Dye 0.1-1.0 ¹A copolymer or any mixtureof copolymers according to any of Application Examples 1, 2, 3, 4, 5, 6,7 or 8. ²Copolymer such as ACUSOL ® 445N from Rohm & Haas orALCOSPERSE ® 725 from Alco. ³Such as SLF-18 POLY TERGENT from the BASFCorporation.

The invention claimed is:
 1. A laundry detergent or cleaning compositionwhich comprises a hydrophobic group-containing copolymer characterizedby having 1 wt % or more but below 50 wt % of a structural unit (a)derived from at least one kind of monomer (A) selected from etherbond-containing monomers represented by the following formulas (1) and(2);

in the above formula (1), R₀ is a hydrogen atom or CH₃ group, R is a CH₂group, CH₂CH₂ group or single bond, X is a number in the range of 0-5(provided X is a number in the range of 1-5 if R is a single bond), andR₁ is an organic group having 6-16 carbon atoms;

in the above general formula (2), R₀ is a hydrogen atom or CH₃ group, Ris a CH₂ group, CH₂CH₂ group or single bond, X is a number in the rangeof 0-5, and R₁ is a hydrogen atom or organic group having 1-20 carbonatoms; and 50 wt % or more but 99 wt % or less of a structural unit (b)derived from a carboxyl group-containing monomer (B) as an essentialconstituting unit, wherein the carboxyl group-containing monomer (B) isacrylic acid or an acrylate salt.
 2. A laundry detergent or cleaningcomposition according to claim 1 wherein the laundry detergent orcleaning composition is selected from the group consisting of liquidlaundry detergent compositions, solid laundry detergent compositions,hard surface cleaning compositions, liquid hand dishwashingcompositions, solid automatic dishwashing compositions, liquid automaticdishwashing compositions, and tab/unit dose form automatic dishwashingcompositions.
 3. A laundry detergent or cleaning composition accordingto claim 1 wherein the detergent or cleaning composition comprises fromabout 1% to about 20% by weight of the hydrophobic group-containingcopolymer composition.
 4. A laundry detergent or cleaning compositionaccording to claim 1 wherein the detergent or composition furthercomprises a surfactant system.
 5. A laundry detergent or cleaningcomposition according to claim 4 wherein the surfactant system comprisesC₁₀-C₁₅ alkyl benzene sulfonates.
 6. A laundry detergent or cleaningcomposition according to claim 4 wherein the surfactant system comprisesC₈-C₁₈ linear alkyl sulfonate surfactant.
 7. A laundry detergent orcleaning composition according claim 4 wherein the surfactant systemfurther comprises one or more co-surfactants selected from the groupsconsisting of nonionic surfactants, cationic surfactants, anionicsurfactants and mixtures thereof.
 8. A laundry detergent or cleaningcomposition according to claim 1 wherein the detergent or compositionfurther comprises cleaning adjunct additives selected from the groupconsisting of enzymes, alkali builders, chelant builders, bleaches,bleaching assisting agents, perfumes, defoaming agents, bactericides,corrosion inhibitors, and mixtures thereof.
 9. A cleaning implementcomprising a nonwoven substrate and the laundry detergent or cleaningcomposition according to claim 1.